United States Office of Air Quality EPA-450/3-85-026
Environmental Protection Planning and Standards October 1985
Agency Research Triangle Park NC 27711
Air
Survey of
Chloroform
Emission Sources
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EPA-450/3-85-026
Survey of Chloroform
Emission Sources
Emission Standards and Engineering Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, NC 27711
October 1985
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This report has been reviewed by the Emission Standards and Engineering Division of the Office of Air
Quality Planning and Standards, EPA, and approved for publication. Mention of trade names or commercial
products is not intended to constitute endorsement or recommendation for use. Copies of this report are
available through the Library Services Office (MD-35), U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina 27711; or, for a fee, from the National Technical Information Services, 5285
Port Royal Road, Springfield, Virginia 22161.
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CONTENTS
Fi gures v
Tables vii
1. Executive Summary 1-1
2. Introduction 2-1
References 2-4
3. Pulp and Paper Industry 3-1
Introduction 3-1
Source Description 3-1
Chloroform Emissions Control 3-6
Control Costs 3-13
Cost-Effectiveness 3-27.
References 3-35
4. Ethylene Dichloride Production 4-1
Introduction 4-1
Source Description 4-4
Chloroform Emissions and Controls 4-8
Conclusions , 4-30
References 4-31
5. Chloroform Production 5-1
Introduction 5-1
Source Description 5-1
Chloroform Emissions and Controls 5-8
Control Costs 5-32
Cost-Effectiveness 5-42
Conclusions - 5-45
References .~~, r 5-47
6. Fl uorocarbon 22 Producti on 6-1
Introduction 6-1
Source Description 6-1
Chloroform Emissions and Controls 6-6
Control Costs 6-17
Cost-Effecti veness 6-21
Conclusions 6-21
References 6-22
7. Oxybisphenoxarsine/1,3 Diisocyanate Manufacturing 7-1
References 7-4
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Contents (continued)
8. Pharmaceutical and Vitamin C Production 8-1
Pharmaceutical Production 8-1
Vitamin C Production 8-2
References " 8-4
9. Trichloroethylene Degradation 9-1
Source Description 9-1
References 9-4
10. Cooling Water 10-1
Source Description 10-1
Chloroform Emissions 10-2
Chi oroform Control Methods 10-4
References 10-5
11. Drinking Water 11-1
Source Description 11-1
Chloroform Formation 11-1
Chi oroform Control Methods 11-9
Chloroform Control Costs 11-16
Chloroform Control Cost-Effectiveness 11-18
Conclusions 11-25
References 11 -26
12. Municipal Wastewater Treatment 12-1
Control Techniques, Costs, and Cost-Effectiveness 12-1
References 12-9
13. Grai n Fumi gati on 13-1
Introduction 13-1
Emissions 13-1
Control Techniques 13-2
References 13-3
iv
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FIGURES
Number Page
1-1 Sources of chloroform emissions 1-3
3-1 Process flow diagram for pulp and paper
manufacturing process 3-4
3-2 A modern bl each sequence " 3-5
4-1 Locations of ethylene dichloride production facilities. 4-3
4-2 Basic operations that may be used in the production of
ethylene dichloride by the balanced process, with
air-based oxychlorination 4-5
4-3 Basic operations that may be used in the production
of ethylene dichloride by the balanced process,
oxygen-based oxychlorination step 4-7
5-1 Locations of chloroform production facilities 5-3
5-2 Basic operations that may be used in the methanol
hydrochlorination/methyl chloride chlorination
process 5-4
5-3 Basic operations that may be used in the methane
chlorination process 5-5
5-4 Summary of estimated current emissions of chloroform
from chloroform production facilities... 5-13
6-1 Locations of fluorocarbon 22 production facilities... 6-3
6-2 Basic operations that may be used in fluorocarbon 22
production 6-4
9-1 Chloroformformation due to photochemical degradation
of trichloroethylene 9-2
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Figures (continued)
Number
11-1
11-2
Schematic of typical water treatment plants
Chloroform formation potential in raw and treated
water
Page
11-2
11-8
12-1 Cost-effectiveness of using improved clarification,
chloramines, or chlorine dioxide during wastewater
treatment r... 12-8
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TABLES
Number
2-1
3-1
3-2
3-3
3-4
3-5
3-6
3-7
3-8
3-9
3-10
3-11
3-12
3-13
3-14
3-15
Chloroform Consumption and Emissions
Pulp and Paper Mill Subcategories
Symbols Representing Bleaching Stages
Average Percent of Chloroform in Bleach Plant
Effluent Formed in Hypochlorite Stages
Chloroform Levels in Pulp and Paper Mill Wastewater
Process Modifications to Model Mills with Existing
B1 each PI ant Sequences
Chloroform Emissions and Emission Reductions from
Market Bleached Kraft Operations
Chloroform Emissions and Emission Reductions from
BCT Bleached Kraft Operations
Chloroform Emissions and Emission Reductions from
Soda and Kraft Fine Bleached Paper Operations
Chloroform Emissions and Emission Reductions from
Papergrade Sulfite Operations
Chloroform Emissions and Emission Reductions from
Miscellaneous Integrated Operations. . .-r.".
Summary of Total Chloroform Production in Pulp and
Paper Mills
Basis for Capital Cost Estimates
Capital and Annual Costs for Bleach Plant
Modifications
Estimated Total Annual Cost of Modifying C-E-H-D
Bleach Sequence for Hardwood to C-E-E -D Sequence
Estimated Total Annual Cost of Modifying C-E-H-D
Bleach Sequence for Softwood to C-E -D-D
Page
2-1
3-2
3-5
3-7
3-8
3-12
3-14
3-15
3-16
3-17
3-18
3-20
3-21
3-22
3-23
3-24
vn
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Tables (continued)
Page
3-16 Estimated Total Annual Cost of Modifying C-E-H Sulfite
Pulp Bleach Sequence to C-E-D for 181 Mg/Day Mill 3-25
3-17 Estimated Total Annual Cost of Modifying C-E-H Kraft
Pulp Bleach Sequence to C-EQ-D for 363 Mg/Day Mill... 3-25
3-18 Estimated Total Annual Cost for Modifying C-E-H-E-D
Kraft Mill Bleach Sequence to C-E -D-E-D for
545 Mg/Day Mill T .- 3-26
3-19 Estimated Total Annual Cost of Modifying C-E-H-D-E-D
Kraft Pulp Bleach Sequence to C-E-E -D-E-D for
545 Mg/Day Mi 11 ? 3-26
3-20 Estimated Annualized Costs and Cost Effectiveness of
Bleach Sequence Modifications in Market Bleached
Kraft Mi 11 s 3-28
3-21 Estimated Annualized Costs and Cost Effectiveness of
Bleach Sequence Modifications in BCT Bleached Kraft
Mi 11 s 3-29
3-22 Estimated Annualized Costs and Cost Effectiveness of
Bleach Sequence Modifications in Soda and Kraft Fine
Bleached Paper Mills 3-30
3-23 Estimated Annualized Costs and Cost Effectiveness of
Bleach Sequence Modifications for Control of
Chloroform in Papergrade Sulfite Mills 3-31
3-24 Estimated Annualized Costs and Cost Effectiveness of
Bleach Sequence Modifications in Miscellaneous
Integrated Mi 11 s 3-32
3-25 Summary of Chloroform Control Cost-Effectiveness 3-34
4-1 Producers of Ethyl ene Di chl ori de 4-2
4-2 Controlled and Uncontrolled Chloroform Emission
Factors for a Hypothetical Facility Producing
Ethylene Dichloride 4-9
4-3 Estimated Chloroform Emissions From Ethylene Dichloride
Production Facilities.. 4-11
4-4 Emission Summary for ARCO/Port Arthur, TX 4-12
viii
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Tables (continued)
Number
4-5
4-6
4-7
4-8
4-9
4-10
4-11
4-12
4-13
4-14
4-15
4-16
4-17
4-18
4-19
4-20
4-21
5-1
5-2
5-3
5-4
Emission Summary for Borden/Geismar, LA
Emission Summary for Diamond Shamrock/Deer Park, TX
Emission Summary for Dow/ Free port, TX
Emission Summary for Dow/Oyster Creek, TX
Emission Summary for Dow/Plaquemine, LA
Emission Summary for DuPont/Lake Charles, LA
Emission Summary for Ethyl /Baton Rouge, LA
Emission Summary for Ethyl /Pasadena, TX
Emission Summary for Formosa Plastics/Baton Rouge, LA...
Emission Summary for Formosa Plastic/Point Comfort, TX..
Emission Summary for Georgia Pacific/Plaquemine, LA
Emission Summary for B.F. Goodrich/LaPorte, TX
Emission Summary for B.F. Goodrich/Calvert City, KY
Emission Summary for B.F. Goodrich/Convent, LA
Emission Summary for PPG/Lake Charles, LA
Emission Summary for Shell /Deer Park, TX
Emission Summary for Vulcan/Geismar, LA
Chloroform Production Facilities ,-. :
Controlled and Uncontrolled Chloroform Emission
Factors for a Hypothetical Chloroform Production
Facility (Methanol Hydrochlori nation/Methyl Chloride
Chlorination Process)
Controlled and Uncontrolled Chloroform Emission Factors
for a Hypothetical Chloroform Production Facility
(Methane Chlorination Process)
Current Chloroform Emissions from Chloroform
Production Facilities
Page
4-13
4-14
4-15
4-16
4-17
4-18
4-19
4-20
4-21
4-22
4-23
4-24
4-25
4-26
4-27
4-28
4-29
5-2
5-10
5-11
5-12
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Tables (continued)
Number Page
5-5 Emission Summary for Diamond Shamrock/Belle, WV 5-14
5-6 Emission Summary for Dow/Freeport, TX 5-18
5-7 Emission Summary for Dow/Plaquemine, LA 5-20
5-8 Emission Summary for Linden/Moundsville, WV 5-22
5-9 Emission Summary for Vulcan/Geismar, LA 5-24
5-10 Emission Summary for Vulcan/Wichita, KS 5-26
5-11 Estimated Best Controls for Chloroform Production
Faci 11 ties 5-28
5-12 Chloroform Emissions from Chloroform Production
Facilities with Estimated Best Controls 5-33
5-13 Model Plant Fugitive Emission Sources 5-36
5-14 Control Costs for Process Fugitives at Chloroform
Producti on Faci 1 i ti es 5-37
5-15 Control Costs for Storage at Chloroform Production
Faci 1 i ti es 5-39
5-16 Control Costs for Handling at Chloroform Production
Facilities 5-41
5-17 Net Annual Control Costs for Estimated Best Control
at Chloroform Production Facilities 5-43
5-18 Cost-Effectiveness of Estimated Best Controls at
Chloroform Production Facilities 5-44
6-1 Fluorocarbon 22 Production Facilities.... r 6-7
6-2 Controlled and Uncontrolled Chloroform Emission Factors
for a Hypothetical Fluorocarbon 22 Production
Faci 1 i ty 6-7
6-3 Chloroform Emissions from Fluorocarbon 22 Production
Faci 1 i ti es 6-8
6-4 Emission Summary for Allied/Elizabeth, NJ 6-9
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Tables (continued)
Number
6-5
6-6
6-7
6-8
6-9
6-10
6-11
7-1
11-1
11-2
11-3
11-4
11-5
11-6
11-7
11-8
11-9
Emission Summary for Allied/El Segundo, CA
Emission Summary for DuPont/Louisville, KY
Emission Summary for Racon/Wichita, KS
Emission Summary for Kaiser/Gramercy, LA
Emission Summary for Pennwalt/Calvert City, KY
Control Costs for Chloroform Storage at Fluorocarbon 22
Plants
Background Data for Control Cost Estimates
Chloroform Emissions Data for Aerojet General
Corporati on
Chloroform Concentration and Population for 137 Cities.
Model Water Plants and Population Served
Annual Chloroform Production in Model Plants at
Various Concentrations
Total Annual i zed Cost of Controlling Chloroform by
Using Chloramines
Total Annual i zed Cost of Controlling Chloroform by
Using Chlorine Dioxide
Total Annual i zed Cost of Controlling Chloroform by
Improvi ng Cl ari f i cati on
Total Annual i zed Cost of Controlling Chloroform by
Modifying Chlorination ~.
Total Annual i zed Cost of Controlling Chloroform
by Using Powdered Act i vated Carbon
Estimated Total Annual Cost and Cost-Effectiveness of
Controlling Chloroform in Drinking Water by
Using Chloramines
Page
6-10
6-11
6-12
6-13
6-14
6-18
6-19
7-2
11-4
11-10
11-10
11-17
11-19
11-19
11-20
11-20
11-22
11-10 Estimated Total Annual Cost and Cost-Effectiveness of
Controlling Chloroform in Drinking Water by Using
Chlorine Dioxide 11-22
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Tables (continued)
Number Page
11-11 Estimated Total Annual Cost and Cost-Effectiveness of
Controlling Chloroform in Drinking Water by Improving
Clarification 11-23
11-12 Estimated Total Annual Cost and Cost-Effectiveness of
Controlling Chloroform in Drinking Water by Modifying
Chi orination 11 -23
11-13 Estimated Total Annual Cost and Cost-Effectiveness of
Controlling Chloroform in Drinking Water by Using
Powdered Acti vated Carbon 11 -24
12-1 Total Annualized Cost of Controlling Chloroform by
Improving Clarification 12-3
12-2 Chloroform Reduction Potential, Costs, and
Cost-Effectiveness of Improved Clarification 12-3
12-3 Total Annualized Cost of Controlling Chloroform by
Using Chloramines 12-5
12-4 Chloroform Reduction Potential, Costs, and
Cost-Effectiveness of Using Chloramines 12-5
12-5 Total Annualized Cost of Controlling Chloroform By
Using Chlorine Dioxide 12-7
12-6 Chloroform Reduction Potential, Costs, and
Cost-Effectiveness of Using Chlorine Dioxide 12-7
xn
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1. EXECUTIVE SUMMARY
This source assessment provides information on emissions and potential
emission controls for chloroform. Chloroform is one of a number of potential
hazardous air pollutants being screened by the U.S. Environmental Protection
Agency to determine if regulatory action under the Clean Air Act is warranted.
Part of this screening procedure includes development of a source assessment
for each chemical. Other portions of the screening procedure include evaluation
of health effects data and pollutant exposure data. Based on these and other
data, the Administrator will determine if chloroform emissions should be
regulated.
Included in this report is information on all significant sources of
chloroform identified to date, emissions, current control, achievable control,
control costs, and cost-effectiveness.
Eleven source categories are discussed to varying degrees in this report.
These are:
• Pulp and paper manufacturing,
• Ethylene dichloride manufacturing,
• Chloroform production,
§ Fluorocarbon 22 production, ~~ _,
• Oxybisphenoxarsine manufacturing,
• Pharmaceutical manufacturing,
• Trichloroethylene photodegradation,
t Chlorination of cooling water,
• Chlorination of drinking water,
• Chlorination of municipal wastewater, and
• Grain fumigation.
1-1
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Emissions data are reported for the eleven source categories listed
above and for Hypalon* manufacturing. Production data on Hypalon- manufacturing
have been claimed to be confidential and are not included in the body of this
report. The source categories listed above emit 8,740 Mg of chloroform
annually. Two sources not listed above include laboratory uses and miscellan-
eous uses. These categories are too disaggregated for reliable emission
estimates to be possible. However, assuming all chloroform production attri-
butable to miscellaneous uses ends up as air emissions, an additional 6,000 Mg
could be emitted to the atmosphere. This estimate is based on a production
level of 159,500 Mg of which 90 percent goes to chlorofluorocarbon 22 production,
5 percent is exported, and approximately 2,000 Mg is used in pharmaceutical
manufacturing.
Of the eleven source categories listed above, four form chloroform by
the reaction of chlorine with organic precursors in water. Chloroform emissions
result from intermedia transfer of chloroform from water to air. These
"inadvertent" emissions account for 74 percent of all chloroform emissions
(Figure 1-1). Although these emissions are secondary, there are methods to
control these releases, the principal method being substitution away from
chloroform forming oxidants such as free chlorine or hypochlorite to compounds
such as chlorine dioxide or chloramines.
Another secondary source of chloroform in the atmosphere is the photode-
gradation of trichloroethylene. Control methods for this source would include
substitution to other halogenated solvents, or use of other cleaning methods.
Direct sources of chloroform emissions result from chloroform production,
its use as a solvent, and its use as an intermediate in the production of
other chemicals such as fluorocarbon 22, which uses-up to 90 percent of all
chloroform produced. Here, conventional control techniques to limit chloroform
emissions would apply.
Source categories which emit chloroform by order of decreasing emissions
are briefly described below. Included in this discussion are potential
controls, costs, and cost-effectiveness.
1-2
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Pulp and Paper Production
Drinking Water Treatment
Pharmaceutical Production
Chloroform Production
Wastewater Treatment
TCE Photodegradation
Cooling Water Treatment
EDC Production
Hypalon Production
Fluorocarbon 22 Production
Grain Fumigation
OBPA Production
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Annual emissions, 103 Mg/yr
Figure 1-1. Sources of Chloroform Emissions.
1-3
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Pulp and Paper Industry
Chloroform air emissions result from wastewater treatment facilities at
pulp and paper mills where chlorine compounds are used in pulp bleaching.
The principal source of chloroform in the pulp and paper industry is the
hypochlorite bleaching stage in pulp bleaching sequences (92 percent of
chloroform produced in pulp bleaching). Chloroform emissions from the five sub-
categories described in this report are estimated to be 3,890 Mg/yr.
A potential chloroform control method is modification of bleaching
sequences to use chlorine dioxide, which forms virtually no-chloroform, and
oxygen as substitutes for hypochlorite. Such modification requires extensive
equipment replacement and therefore would disrupt production and be very
expensive. Annualized costs for controls range from a net savings of
$25,000/yr for a 545 Mg/day kraft pulp C-E-H-D-E-D sequence to $5,550,000/yr
for a 363 Mg/day C-E-H kraft pulp bleach sequence.9 The cost-effectiveness of
control ranges from $416,900/Mg to a net savings of $l,400/Mg, with a mean
cost-effectiveness for all mills of $85,600/Mg.
Drinking Water
Chiorination of drinking water for disinfection produces chloroform in
many water supply systems. Approximately 1,900 Mg/yr of chloroform evaporate
from water to air as a result of water supply chlorination.
Five chloroform control techniques have been identified by the Office of
Drinking Water as "generally available." These potential controls are: use
of chloramines, use of chlorine dioxide, improving existing clarification,
moving the point of chlorination, and use of powdered activated carbon. The
average total annualized control costs for the largest model plant range from
$99,000 to $3,093,000 per year. The cost-effectiveness of controls depends
on the amount of chloroform controlled, and ranged from $2,800/Mg for a
100 yg/1 decrease in a large treatment plant to $877,000/Mg for a 10 pg/1
decrease in a small treatment plant.
aRefer to page 3-5 for an explanation of these symbols.
1-4
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Chloroform Production
There are six chloroform production facilities currently operating in
the U.S., with a current estimated chloroform emission total of 458 Mg/yr.
Sixty percent of these emissions are from fugitive sources such as fugitive
leaks from process components, losses from loading chloroform into transport
•*
vessels, and several secondary emission sources. The remaining 40 percent is
due mostly to chloroform storage, with significant process vent emissions at
a few plants. Available control technology (ACT) could be used to reduce
emissions to 144 Mg/yr, mostly by controlling process fugitive sources and
storage tanks. After ACT, emissions would consist mostly of remaining
process fugitives, uncontrolled secondary emissions and in-process storage
not covered by ACT controls on main product storage tanks. For storage,
handling, and some plants' process vents, ACT consists of refrigerated
condensers. Process fugitive emissions can be controlled by a combination of
monthly inspection and maintenance, and additional equipment specifications
for some process components.
The total net annual cost for implementation of ACT for chloroform
production facilities is estimated at $525,000. About $410,000 of this total
is for control of chloroform handling, the most expensive ACT with an average
cost-effectiveness of $9,100/Mg. Almost all of the remaining cost is divided
between process fugitive controls ($51,000/yr; $380/Mg) and storage controls
($59,000/yr; $630/Mg). The net costs and cost-effectiveness of individual
controls varies significantly, due to differences in chloroform recovery
credits and the level of controls already in place. Total estimated annual
costs per plant vary from $12,300 for a plant with most ACT controls in
place, to $135,000 for a plant requiring two separate handling control systems
as well as other controls. Cost-effectiveness at the plant level is estimated
to range from $960/Mg to $5,800/Mg.
Municipal Wastewater Treatment
It is estimated that 424 Mg of chloroform are generated and released to
the environment as a result of wastewater treatment and disinfection. On
average, the amount of chloroform in wastewater decreases by 4.6 ug/1 from
influent to secondary effluent. With 9.2081 x 10 liters treated per day,
1-5
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national emissions from wastewater treatment are 155 Mg/yr. In addition,
chlorination of treated effluent increases chloroform concentrations in
wastewater by 8 ug/1. Thus, an additional 269 Mg of chloroform are generated
annually as a result of disinfection of effluent.
Methods of control to reduce chloroform formation due to disinfection
include precursor removal prior to chlorination (improved clarification), or
use of a disinfectant that does not form chloroform (use of chloramines or
chlorine dioxide). Control efficiency ranges from 37 to 90 percent depending
on the method used. Annualized control costs range from $8,000 for a small
plant using chloramines to $1,120,000 for a large plant using improved
clarification. Cost-effectiveness ranges from $38,700/Mg for a large plant
using chloramines to $1,560,000/Mg for a small plant using improved clarification,
Trichloroethylene Photodegradation
Chloroform forms in the atmosphere as a result of photodecomposition of
trichloroethylene. It is estimated that for every ppm of trichloroethylene
emitted to the atmosphere, 7 ppb of chloroform are formed. In 1982, 67,200 Mg
of trichloroethylene were emitted to the atmosphere, resulting in the formation
of 420 Mg of chloroform. Methods of control include use of alternative
halogenated solvents for solvent degreasing, or alternative cleaning methods.
Cooling Water
Chloroform is formed when cooling water in steam electric plants is
chlorinated to prevent biofouling in heat-exchange equipment. An estimated
197 to 263 Mg/yr of chloroform are produced and emitted from cooling water
chlorination.
Potential chloroform control could be attainetLby using alternative
biofouling control methods such as other oxidizing chemicals, nonoxidizing
biocides, and mechanical cleaning. None of these alternatives is used widely
at this time.
Ethylene Pi chloride Production
There are a total of 20 ethylene dichloride production facilities in the
U.S. It is estimated that emissions of byproduct chloroform from these
facilities are currently about 173 Mg/yr. The main emission sources include
oxychlorination reactors, purification and separation columns, and a few
1-6
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reported instances of emissions from liquid waste storage or disposal and
other waste-treatment steps. At all but two plants, all reactor and column
vents are controlled by thermal oxidation, which has efficiency of 98 percent
or greater. Applying a similar level of control to these vents at the two
remaining plants is estimated to reduce total chloroform emissions to 117 Mg/yr.
The majority of this emission reduction is due to uncontrolled column vents
at one plant. Costs and cost-effectiveness were not estimated for the few
remaining potential controls due to the high level of existing control in the
industry, and unavailability of sufficient plant-specific data.
Fluorocarbon 22 Production
There are currently six facilities in the U.S. that produce fluorocarbon 22
on a routine basis. These facilities are estimated to emit about 50 Mg,
almost entirely from storage of chloroform feedstock. With 95 percent control
of all storage emissions by refrigerated condensers, this total can be reduced
to about 5.7 Mg/yr. This would involve installation of condensers at four plants,
at a total net annual cost of $122,300. For individual plants, these controls
are estimated to cost from $2,200/Mg to $4,100/Mg, with an industry-wide
average of $2,800/Mg.
Oxybisphenoxarsine/1,3-Diisocyanate Manufacture
Oxybisphenoxarsine (OBPA) and 1,3-diisocyanate are both produced by
Aerojet General Corporation in Sacramento, California. OBPA is a fungicide
which is combined with rubber to prevent mold growth on gaskets and seals.
1,3-Diisocyanate is an intermediary in the production of polyurethane resins.
Combined chloroform emissions from these two processes amount to 23.77 Mg/yr.
Both sources are controlled by carbon adsorption. ""A-third source of chloroform
emissions is a deaerator of hazardous waste prior to deep well injection.
Reported emissions from this source are 25.5 Mg/yr. There are no known
controls for this source.
Grain Fumigation
Chloroform has been used as a carrier in grain fumigation. Vulcan
Materials Company markets Chlorofume FC 30 Grain Fumigant containing 72.2 percent
chloroform, 20.4 percent carbon disulfide, and 7.4 percent ethylene dibromide.
In 1981, 28.4 Mg of chloroform were used in this manner.
1-7
-------
Because of the recent cancellation of pesticide products containing EDB
(49 FR 4452), it is not known whether Vulcan plans to reformulate Chlorofume®
without EDB. If so, a potential substitute to chloroform as a carrier would
be carbon tetrachloride, which is used as a carrier in virtually all other
fumigants.
Pharmaceutical Manufacture
Specific data on uses of chloroform in the pharmaceutical industry are
very limited. A recent survey conducted by the Pharmaceutical Manufacturers
Association indicates that total direct air emissions fronTthis source
category are on the order of 1000 Mg/yr. This total includes the known use
of chloroform as a solvent in production of Vitamin C at one Hoffman-LaRoche
plant, where total emissions are estimated at about 220 Mg/yr. Further
information is not available on one other very small Vitamin C production
facility (Pfizer, Groton, CT), or on other uses of chloroform in pharmaceutical
manufacturing.
1-8
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2. INTRODUCTION
The purpose of this report is to provide information on sources of air
emissions of chloroform. Chloroform is one of a number of chemical compounds
being screened by the U.S. Environmental Protection Agency to determine
whether they should be regulated under the Clean Air Act. Results of this
source assessment will be combined with other information, such as health
effects data and exposure data, to form a comprehensive analysis of the
threat to public health posed by chloroform. Based on all the information
available, the Administrator will then decide whether chloroform should be
regulated and if so, which regulatory mechanism under the Clean Air Act
should be used. The information presented in this report includes data on
emission sources of chloroform, current emission and emission control levels,
emission point coordinates, and an analysis of emission reduction achievable
on existing sources through use of best available control technology.
In 1982, it was estimated that 159,500 Mg of chloroform was produced.
Of this amount, approximately 90 percent is used in the production of fluoro-
carbon 22, five percent is exported, and the remainder is used by miscellaneous
sources such as laboratories, pharmaceutical companies, and dye and pesticide
companies. Of the 159,500 Mg produced, known annual emissions from primary sources
amount to approximately 1,840 Mg, or slightly greater than one percent of
production (Table 2-1). Most emissions of chloroform to the environment
result from its inadvertent formation and release (6,900 Mg/yr). Four of the
source categories which contribute to its inadvertent formation and release
form chloroform by the reaction of chlorine with organic precursors in water.
Chloroform emissions from these four categories result from the intermedia
transfer of chloroform from water to air and amount to 6,480 Mg per year.
These categories include pu.lp and paper manufacturing, drinking water treatment
plants, wastewater treatment plants, and cooling water treatment by power
plants. Although these emissions are secondary, there are methods to control
2-1
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TABLE 2-1. CHLOROFORM CONSUMPTION AND EMISSIONS
Chloroform Chloroform
consumed, Mg/yr emitted, Mg/yr
PRIMARY SOURCES
Pharmaceutical production 2,000a 1,000
Chloroform production - . - 458
Ethylene dichloride production - 173
Hypalon® production b 79.7
Fluorocarbon 22 production 144,000 50.2
Oxybisphenoxarsine production c 49.3
Grain fumigation 28.4 28.4
Subtotal 146,000 1,838.6
SECONDARY SOURCES
Water Sources
Pulp and paper production - 3,890
Drinking water treatment - 1,900
Wastewater treatment - 424
Cooling water treatment - 263
Air Sources
Trichloroethylene - 420
photodegradation
Subtotal - 6,897
Total 146,000 __ - 8,735.6
Estimated
Confidential
GUnknown
2-2
-------
these releases, including substitution away from chloroform-forming oxidants
such as free chlorine or hypochlorite to compounds such as chlorine dioxide
or chloramines.
Each chapter in the document describes a chloroform source category.
Chapters include pulp and paper manufacturing; ethylene dichloride production;
chloroform production; fluorocarbon production; oxybisphenoxarsine/diisocyanate
manufacture; pharmaceutical manufacture; trichloroethylene photodegradation;
evaporation from boiler cooling water, drinking water and municipal wastewater;
and grain fumigation.
One source category not discussed in this document is laboratory usage.
There are approximately 109,700 laboratories in the U.S. Chloroform is used
in hospital, industrial, government, and university laboratories. It is used
as a general reagent and in high pressure liquid chromatography (HPLC).
However, aggregate data on the amount of chloroform used by laboratories
could not be quantified for two reasons. First, chloroform is sold to labora-
tories by a variety of sources. Some is purchased directly from producers;
however, most is sold by producers to distributors who buy in bulk and then
repackage or reformulate the chloroform for a specific type of end use (i.e.
general reagent vs. HPLC). Because the chain of distribution is so disaggregated,
there is no production or distribution source to provide aggregate data on
chloroform in laboratories. One distributor stated that while the company
keeps records on "solvents" as a category, it does not keep detailed records
2
for specific solvents.
The second reason for lack of aggregate data stems from the fact that
laboratorie's do not represent a homogeneous user category. Consequently,
there is no central source of information from which-to obtain such data for
all laboratory use. However, chloroform use in laboratories does appear to
be widespread. One university reported that in a survey on carcinogenic
chemicals used in its 67 laboratories, chloroform was the most widely used,
appearing in 53 laboratories.
2-3
-------
REFERENCES
1. Phase I Study: Profile of Laboratories with the Potential for
Exposure to Toxic Substances. Prepared by Booz, Allen and Hamilton
for Occupational Safety and Health Administration, Office of Regulatory
Analysis, Washington, DC. March 1, 1983.
2. Telephone conversation between H. Rollins, GCA Corporation and J. Richards,
J.T. Baker Chemical Company, Phillipsburg, New Jersey. November 8, 1982.
3. Survey of the use of Chemical Carcinogens in University Laboratories.
University of North Carolina at Chapel Hill. Chapel Hill, North Carolina.
(no date).
2-4
-------
3. PULP AND PAPER INDUSTRY
INTRODUCTION
The pulp and paper industry is the largest chloroform emissions source
category, accounting for approximately 40 percent of chloroform air emissions
in the United States. Chloroform is produced indirectly in process water
during the bleaching of wood pulp by the reaction of chlorine and its compounds
2
with lignins in pulp. Chloroform formed in process water subsequently
evaporates to the atmosphere during both the treatment of process wastewater
and following treatment (from discharged mill effluent). Chloroform evaporation
from process water and wastewater is the source of chloroform air emissions
discussed in this chapter.
This chapter presents an overview of the pulp and paper industry, chloro-
form formation and fate in pulp bleaching processes, methods to reduce chloro-
form emissions, emission control costs for representative model plants,
emissions estimates for pulp mills, and cost effectiveness of emissions
control.
SOURCE DESCRIPTION
Industry Overview
•
The U.S. Environmental Protection Agency's Effluent Guidelines Division
has identified 706 operating facilities involved in the manufacture of pulp,
paper, and paperboard products. The mills vary in size, age, location, raw
material usage, products manufactured, production processes employed, and
effluent treatment systems used. The pulp, paper, and paperboard industry
consists of 3 major segments: integrated mills (where pulp alone or pulp and
paper or paperboard are manufactured on-site); non-integrated mills (where
paper or paperboard is manufactured but no pulp is made on-site); and secondary
fibers mills (where wastepaper is used as the primary raw material). The
Effluent Guidelines Division subcategorized mills with respect to raw materials,
processing sequences, and types of end products made. These subcategories,
which have been adopted for this report, are listed in Table 3-1.
3-1
-------
TABLE 3-1. PULP AND PAPER MILL SUBCATEGORIES
Integrated Segment
Dissolving Kraft
Market Bleached Kraft
BCT Bleached Kraft
Soda
Unbleached Kraft
- Linerboard
- Bag
Semi-Chemical
Unbleached Kraft & Semi-Chemical
Dissolving Sulfite Pulp
- Nitration
- Viscose
- Cellophane
- Acetate
Papergrade Sulfite
Groundwood - Thermo-Mechanical
Groundwood - CMN Papers
Groundwood - Fine Papers
Nonintegrated Segment
Nonintegrated - Fine Papers
Nonintegrated - Tissue Papers
Nonintegrated - Lightweight Papers
- Lightweight
- Electrical
Nonintegrated-Filter and Nonwoven Papers
Nonintegrated-Paperboard
Mill Groupings:
*Integrated Miscellaneous including:
- Alkaline-Miscellaneous
- Groundwood Chemi-Mechanical
- Nonwood Pulping
*Secondary Fiber-Miscellaneous
*Nonintegrated-Miscellaneous
Secondary Fibers Segment
Deink
- Fine Papers
- Tissue Papers
- Newsprint
Tissue from Wastepaper
Paperboard from Wastepaper
Wastepaper - Molded Products
Builders' Paper and Roofing Felt
Groupings of miscellaneous mills, not subcategories.
3-2
-------
Pulping and Bleaching Process
As shown in Figure 3-1, pulp is produced by a series of steps which
includes raw material preparation, pulping, and bleaching. Bleaching generally
is followed by either papermaking or bundling of pulp for shipment to another
papermaking mill. The major raw material for pulp manufacturing is wood.
The preparation of wood for pulping includes log washing, bark removal, and
chipping. Pulping is the process in which wood fibers are separated by
dissolving or breaking the lignin holding the fibers together. At the end of
this process, the pulp mass is brown or deeply colored due to the presence of
lignins and resins. Thus, it must be bleached if a white or light-colored
product is to be produced.
The purification and whitening of pulp is achieved in a series of bleaching
stages. Each stage consists of mixing the pulp over time with chemicals and
heat, and washing the pulp after reaction to remove chemical impurities.
Each stage may vary according to the chemical added, pulp consistency, temperature,
time, and pH. Bleach plants range from a single stage to as many as nine or
ten stages. Different bleaching stages are commonly represented by symbols
such as those shown in Table 3-2. The most common bleaching agents used to
bleach pulp are chlorine, sodium or calcium hypochlorite, and chlorine dioxide
(used in various combinations of stages). A simplified drawing of a typical
bleaching sequence is shown in Figure 3-2. As the figure shows, chlorine (C)
and chlorine dioxide (D) bleaching stages are separated by washing and alkaline
extraction (E) stages.
In the chlorine stage, chlorine combines with lignins in the pulp forming
chlorinated lignins. The chlorination reaction is^extremely rapid, requiring
as little as five minutes for completion. After the pulp has b€'en saturated
with chlorine, it is washed and sent to the caustic extraction stage.
Oxidized lignin is solubilized in the caustic extraction stage. In this
stage, the phenolic-OH group in lignin dissolves in alkaline solution and
chlorinated lignins are degraded into smaller fragments.
3-3
-------
PULP LOG
WOOD
PREPARATION
ACID SULFITE LIQUOR
ALKALINE SULFATE L1QUOR-
(KRAFT)
NEUTRAL SULFITE LIQUOR
DEBARKED LOG
(GROUNDWOOD)
CHEMICAL
REUSE
WHITE WATER OR
FRESH WATER
WHITE WATER OR
REUSE WATER
BLEACHING AND OTHER
NECESSARY CHEMICALS
FRESH WATER OR WHITE
WATER REUSE
FILLERS
DYE
SIZE
ALUM
STARCH
FRESH WATER OR
WHITE WATER REUSE
COATING CHEMICALS
WOOD
CHIPS
PULPING
CRUDE
PULP
EVAPORATION
(HEAT GENERATION AS
A BYPRODUCT)
KRAFT a NEUTRAL
SULFITE RECOVERY
•CONDENSATE-
WASHING
SCREENING
THICKENING
UNBLEACHED PULP
BLEACHING
STOCK
PREPARATION
PAPER
MACHINE
FINISHING 8
CONVERTING
CHLOROFORM IN
BLEACHING
EFFLUENT
CHLOROFORM
EMISSIONS
EFFLUENT
TREATMENT
FINISHED PAPER
PRODUCTS
Figure 3-1. Process flow diagram for pulp and paper manufacturing process.
3-4
-------
TABLE 3-2. SYMBOLS REPRESENTING BLEACHING STAGES
8
Name of
stage
Symbol
Chemical
used
Chlorination
Caustic Extraction
Hypochlorite
Chlorine Dioxide
Oxygen
Peroxide
Ozone
C
E
H
D
0
P
Z
Chlorine gas or chlorine water
Sodium Hydroxide solution
Sodium or Calcium hypochlorite
Water solution of Chlorine Dioxide
Oxygen gas and alkali
Hydrogen Peroxide (50% sol.)
Gaseous ozone (2% in Oxygen)
J©
-------
Hypochlorite bleaching decolorizes and solubilizes the residual lignin,
dyes, and other impurities in fiber. The bleaching reaction proceeds rapidly
at first but slows down before all the lignin has reacted. Hypochlorite
oxidizes cellulose (wood fiber) as well as lignin and other impurities. The
oxidation of wood fibers is undesirable because it weakens the fibers and the
paper products made from them. The severity of cellulose oxidation depends
on temperature, pulp consistency, pH, and the amount of residual lignin
compared to hypochlorite concentration.
Chlorine dioxide is often used in the final two bleaching stages in the
more modern bleach plants, as shown in Figure 3-2. Bleaching with chlorine
dioxide is carried out in an acidic solution, and typically degrades cellulose
much less than hypochlorite.
Chloroform Formation and Fate
The use of calcium or sodium hypochlorite for bleaching pulp is recognized
as the major source of chloroform in the pulp and paper industry. Data
presented in Table 3-3 show that effluent from hypochlorite bleach stages
generally contains much higher chloroform concentrations than effluent from
other stages.
Effluent from bleaching operations typically is discharged to on-site
pulp mill wastewater treatment plants. Table 3-4 presents chloroform levels
measured in some mill wastewater treatment plant influents and effluents for
various subcategories of pulp and paper mills. The influent and effluent
chloroform measurements in the table show a sharp decrease in wastewater
19
chloroform concentrations during treatment, a trend attributed to evaporation.
The nine subcategories in which chlorine compounds are used as bleach are noted
in the table.
CHLOROFORM EMISSIONS CONTROL
Control Alternatives
Emissions of chloroform from pulp and paper mills may be controlled by
modifying the bleaching process to reduce or prevent chloroform formation.
Because wastewater treatment plants at pulp mills treat large quantities of
wastewater and often use several acres of stabilization ponds, capture of
chloroform from treatment plants is not feasible by any available technology.
3-6
-------
TABLE 3-3. AVERAGE PERCENT OF CHLOROFORM IN BLEACH PLANT EFFLUENT
FORMED IN HYPOCHLORITE STAGES3
Bleach
plant
A
B
C
D
E
F
Chloroform
from
hypochlorite
stages,
kg/Mg of pulp
0.54
1.78
1.65
0.18
0.25
1.12
Total
chloroform
from bleach plant
kg/Mg of pulp
0.62
1,84
1.68
0.26
0.43
1.16
Percent
chloroform
from
hypochlorite
stages
__
--
--
—
--
__
TOTAL
5.52
5.99
92
Reference 11.
3-7
-------
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3-8
-------
Process modification consists of replacing hypochlorite with a chemical
such as chlorine dioxide, which produces virtually no chloroform. Different
bleaching chemicals have characteristic effects on pulp fibers, and for some
special applications hypochlorite bleaching must be retained (the bleaching
of broke, for example, which is pulp that is not baled and is reprocessed).
However, chlorine dioxide can be used in a bleach sequence to obtain a bright-
ness roughly equal to hypochlorite bleaching, and with better strength
characteristics. Again, this is due to chlorine dioxide's ability to attack
lignin without significantly degrading the wood fibers. The industry trend
the past 15 years has been to design new pulp mills to bleach with chlorine
14
dioxide rather than hypochlorite.
Molecular oxygen, which does not react to form chloroform, has been used
successfully in pulp bleaching as a separate oxidizing stage and as a chemical
supplement to the alkaline extraction stage. Oxygen, used either in a separate
oxidizing stage or as a supplement to the alkaline extraction stage, can be
considered a partial substitute for hypochlorite in bleaching.
Four categories - dissolving sulfite pulp, dissolving kraft pulp, deink
tissue, and deink fine paper - were assumed to continue using hypochlorite
for technical reasons. Thus, no emission reductions are presented for these
categories.
Dissolving pulps must be considered a completely separate group of
fibers because the conversion of fibers into their final state involves a
complex bleaching and purification process which often involves change of
phase. Bleach sequences for dissolving pulps were designed with hypochlorite
stages playing an important part in pulp treatment. The selection of a
substitute for hypochlorite in bleaching dissolving j^ulps poses a technical
problem which is beyond the scope of this project.
The bleaching requirements of deink pulps vary widely depending on the
proportions of groundwood, unbleached chemical fibers, and colored paper.
Often a single stage of hypochlorite is sufficient, but as many as five
stages are feasible for large mills. Hypochlorite is used because it is
relatively inexpensive, easy to handle, and non-corrosive. Because the raw
3-9
-------
materials and the bleaching requirements in deink mills vary widely, an
analysis of feasible substitutes for hypochlorite in these mills is beyond
the scope of this project. Thus, mills in the deink categories were assumed
to continue using hypochlorite.
Scope of Modifications
In replacing hypochlorite at a given pulp mill, several things must be
considered. Bleach sequences are designed to produce a specific end product
or variety of products. The sequence used depends on the type of wood used,
the brightness and strength characteristics desired, the degree of flexibility
desired in the sequence, and the cost. Replacing hypochlorite not only
changes the sequence, but also changes the overall effect the interrelated
stages have on the pulp. Thus, replacing hypochlorite entails more than
merely substituting another bleaching chemical. It involves replacing an
entire sequence using hypochlorite with a sequence not using hypochlorite,
18
considering the end products and other parameters mentioned above.
While a new pulp mill bleach sequence can readily be designed to use
chlorine dioxide (omitting hypochlorite), differences between the two chemicals
do not allow simple one-for-one replacement of hypochlorite with chlorine
dioxide in existing mills. Because chlorine dioxide bleaches most effectively
at a pH of 3.6, its solution is much more corrosive than typical hypochlorite
19
bleaching solution, which has a pH of 11. Thus, in an existing pulp mill,
the hypochlorite equipment, such as bleach towers, washers, thick stock
pumps, seal tanks, and piping, can not withstand the acidic chlorine dioxide
18
and must be replaced.
In addition to the difference in the pH of their bleaching solutions,
chlorine dioxide and hypochlorite differ in their chemical action on pulp.
The alkalinity of a hypochlorite bleaching solution allows the reaction
products to dissolve much more readily than in the acidic chlorine dioxide
solution. When hypochlorite is used, lignin reacts and goes into solution,
exposing more lignin for further chemical attack. Chlorine dioxide is most
effective when the pulp is washed in an alkaline solution between bleach
stages to remove oxidized lignin so that more layers of lignin can be attacked.
Consequently, use of chlorine dioxide may require more alkaline extraction
20
stages in the bleach sequence than hypochlorite.
3-10
-------
Generation of chlorine dioxide must also be considered. Chlorine dioxide
is highly unstable, and consequently is manufactured on-site wherever it is
used in a pulp bleaching operation. To provide the amount of chlorine dioxide
required in typical bleaching operations, a chlorine dioxide production
process is needed, as well as raw chemical storage tanks, unloading facilities,
pumps, and piping. Some pulp mills use both hypochlorite and chlorine dioxide
in bleaching pulp, while other mills using hypochlorite use no chlorine
dioxide and therefore have none of the equipment on-site needed to produce
chlorine dioxide. For pulp mills with chlorine dioxide production equipment,
the additional chlorine dioxide required to replace hypochlorite may be
produced from existing excess capacity; however, excess capacity may not be
available in every mill. Where chlorine dioxide is not used in bleaching,
replacement of hypochlorite with chlorine dioxide would require the purchase
and installation of a chlorine dioxide production plant and the appurtenances
18
list above.
In those mills where oxygen could replace or partially replace hypochlorite
as a bleaching agent, equipment for adding and mixing oxygen into the pulp
would be needed, as well as a tank for storing liquid oxygen on-site.
Model Mills
Because pulp mills vary in physical design and type of end product, the
replacement bleach sequence should be developed on a case-by-case basis.
However, several different pulp mills use a few common sequences. For this
analysis, pulp mills were categorized not only based on end product, but on
bleach sequence as well. The most common bleach sequences utilizing hypochlorite
were identified and then grouped according to their manufacturing capacity.
As a result, a large portion of U.S. mills were categorized based on bleach
sequence and production capacity. Each category is represented by a "model"
pulp mill characterized by a bleach sequence (utilizing hypochlorite) and
production capacity. Manufacturers of pulp bleaching equipment were contacted
to obtain information on feasible substitute sequences utilizing chlorine
1821
dioxide and oxygen. ' The model mills, their substitute bleach sequences,
and a description of the modifications involved are presented in Table 3-5.
3-11
-------
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3-12
-------
Emissions and Emissions Reduction
Based on the chloroform concentration data presented in Table 3-4,
chloroform emissions from each mill in the five subcategories for which
controls were considered were calculated based on estimated wastewater flow
and chloroform concentration. Estimated chloroform emissions for each mill
are presented in Tables 3-6 through 3-10." Total annual chloroform emissions
from all mills in these subcategories are estimated to be 3,340 Mg/yr.
Total chloroform production, based on influent chloroform concentrations
in mills in all nine subcategories which bleach with chlorine or chlorine-containing
compounds, is presented in Table 3-11. Approximately 3,890 Mg/yr of chloroform
are produced from pulp bleaching and emitted from either the mill sites or
the body of water receiving wastewater discharges.
Based on the data presented in Table 3-3, chloroform emissions from each
pulp mill were assumed to be reduced 92 percent as the result of process
modification. The estimated chloroform emission reductions at each mill are
presented in Tables 3-6 through 3-10. Emission reductions range from 4.4 Mg/year
to 154.5 Mg/year.
CONTROL COSTS
Control costs were estimated for eight model mills based on the modifica-
tions described in Table 3-5. The control costs for existing pulp mills were
drawn from the costs for the model mill that most closely matched the bleach
sequence and size of the existing mill. Where the model mills did not represent
an existing mill, the costs for that mill were computed separately.
Unit chemical costs and the basis for the capital recovery factor are
presented in Table 3-12. The capital costs that provide the basis for the
model mill estimates are presented in Table 3-13. The chemical costs and
equipment costs for bleach sequence modifications were obtained from two
1821 22
leading pulp bleaching equipment manufacturers and from the pulp industry. °»t'>"
The cost from the pulp industry were obtained by the National Council for Air
and Stream Improvement (NCASI) from questionnaires sent to several major pulp
22
manufacturing companies in various regions of the U.S. All costs are in
mid-1983 dollars. Tables 3-14 through 3-19 present the estimated total
3-13
-------
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3-17
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3-19
-------
TABLE 3-11. SUMMARY OF TOTAL CHLOROFORM PRODUCTION
IN PULP AND PAPER MILLS
Total chloroform Total chloroform
Mill subcategory production (kg/day) production (Mg/yr)
Market Bleached Kraft
BCT Bleached
Soda and Kraft Fine Paper
Papergrade Sulfite
Miscellaneous Integrated
Dissolving Kraft
Dissolving Sulfite
Deink Fine
Deink Tissue
TOTAL
l,414.6a
l,631.2a
l,547.9a
2,176.4a
2,835.4a
382. 6b
216. 5b
338. Ob
104. lb
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595.4
565.0
794.4
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139.6
79.0
123.4
38.0
3,886.0
aBased on the influent chloroform concentrations presented in Tables 3-6
through 3-10.
Calculated by multiplying individual mill wastewater flows by average or
measured wastewater influent chloroform concentrations. Data were
obtained from verification sampling data in Docket WH-552, available to
the public at the Public Information Reference Unit, U.S. Environmental
Protection Agency, Washington, DC.
3-20
-------
TABLE 3-12. BASIS FOR CAPITAL COST ESTIMATES.
1. Capital recovery factor for capital 0.128 x capital
charges (10 percent interest and
16-year life)
2. Annual maintenance charges 0.05 x capital
3. Annual miscellaneous charges 0.04 x capital
(taxes, insurance, administration)
TOTAL ANNUALIZED COST FACTOR 0.218 x capital
4. Chemical costs (dollars/Mg)a
• Hypochlorite 385b
0 Chlorine dioxide 1,3255
• Oxygen 225
• Sodium hydroxide 250
aCosts are based on comments from industry supplied by NCASI (mid-1983 dollars)
While actual costs can be significantly lower or higher, this figure
represents a reasonable average of costs quoted in the comments received.
This cost assumes no recovery credit for by-product hypochlorite
produced in scrubber controlling chlorine emission from C10? generating
process.
Includes cost of magnesium salts added for resistance to fiber attack.
3-21
-------
TABLE 3-13. CAPITAL AND ANNUAL COSTS FOR BLEACH PLANT MODIFICATIONS18'21'22
(mid-1983 dollars)
1.
Cost items for pulp mills
Install chlorine dioxide bleaching stage in place of hypochlorite
bleaching stage
t 181 Hg/day mill
• 363 Mg/day mill
• 545 Mg/day mill
Capital cost
($1000)
3,000
3,500
4,000
Annual cost
(SIOOO)3
654
763
872
2. Install additional chlorine dioxide generating plant on site
(5.45 Mg/day C102 production capacity) 4,200 916
3. Storage tanks, handling facilities, pumps, and piping for chlorine
dioxide and chlorine dioxide feedstock chemcials at mills where
chlorine dioxide is not presently used
• 181 Mg/day mill 750 164
• 363 Mg/day mill 1,000 218
4. Install oxygen addition equipment to caustic extraction stage 500 109
(All mill capacities)
aCapital costs annualized with a factor of 0.218, the sum of the factors for capital recovery, maintenance, and
miscellaneous charges presented in Table 3-12.
3-22
-------
TABLE 3-14. ESTIMATED TOTAL ANNUAL COST OF MODIFYING C-E-H-D
BLEACH SEQUENCE FOR HARDWOOD TO C-E-E -D SEQUENCE
(mid-1983 dollars) °
Mill size (Mg/day) Annual costs
and cost items ($1000)
181 Mg/day
1. Hypochlorite stage converted to caustic extraction
stage with oxygen addition $ 109
2. Additional chemicals:
• Sodium hydroxide, 8 kg/Mg _ 132
t Chlorine dioxide 2 kg/Mg 175
• Oxygen, 4 kg/Mg 59
3. Rental of oxygen storage tank • 12
4. Hypochlorite cost, as savings, 12.5 kg/Mg - 318
TOTAL NET COST $ 168
545 Mg/day^
1. Hypochlorite stage converted to caustic extraction
stage with oxygen addition $ 109
2. Additional chemicals:
0 Sodium hydroxide, 8 kg/Mg 398
• Chlorine dioxide, 2 kg/Mg 526
0 Oxygen, 4 kg/Mg 177
3. Rental of oxygen storage tank 12
4. Hypochlorite cost, as savings, 12.5 kg/Mg - 957
TOTAL NET COST $ 265
3-23
-------
TABLE 3-15. ESTIMATED TOTAL ANNUAL COST OF MODIFYING C-E-H-D
BLEACH SEQUENCE FOR SOFTWOOD TO C-E -D-D
(mid-1983 dollars) °
Mill size (Mg/day) Annual costs
and cost items ($1000)
181 Mg/day
1. Chlorine dioxide bleach stage, installed $ 654
2. Chlorine dioxide generator, installed 916
3. Chlorine dioxide chemical, 5 kg/Mg 437
4. Oxygen handling and mixing equipment, installed 109
5. Oxygen added to caustic extraction stage, 5 kg/Mg 74
6. Oxygen storage tank rental 12
7. Hypochlorite cost, as savings, 20 kg/Mg - 509
TOTAL NET COST $ 1,693
545 Mg/day
1. Chlorine dioxide bleach stage, installed $ 763
2. Chlorine dioxide generator, installed 916
3. Chlorine dioxide chemical, 5 kg/Mg 1,315
4. Oxygen handling and mixing equipment, installed 109
5. Oxygen added to caustic extraction stage, 5 kg/Mg 222
6. Oxygen storage tank rental 12
7. Hypochlorite cost, as savings, 20 kg/Mg -1.532
TOTAL NET COST $ 1,805
3-24
-------
TABLE 3-16. ESTIMATED TOTAL ANNUAL COST OF MODIFYING C-E-H SULFITE
PULP BLEACH SEQUENCE TO C-E-D FOR 181 Mg/DAY MILL
(mid-1983 dollars)
Annual costs
Cost items ($1000)
}. Chlorine dioxide bleach stage, installed $ 654
2. Chlorine dioxide generator, installed 916
3. Chlorine dioxide chemical, 5 kg/Mg 524
4. Storage tanks, handling facilities, pumps, and piping for chlorine
dioxide feedstock chemicals ~ 164
5. Hypochlorite cost, as savings, 15 kg/Mg - 382
TOTAL NET COST $ 1,876
TABLE 3-17. ESTIMATED TOTAL ANNUAL COST.OF MODIFYING C-E-H KRAFT
PULP BLEACH SEQUENCE TO C-E -D FOR 363 Mg/DAY MILL
(mid-1983 dollars)
'o
1.
2.
3.
4.
5.
6.
7.
8.
Cost items
Oxygen handling and mixing equipment
Oxygen added to caustic extraction stage, 5 kg/Mg
Oxygen storage tank rental
Chlorine dioxide bleach stage, installed
Chlorine dioxide generator, installed
Chlorine dioxide chemical, 6 kg/Mg
Storage tanks, handling facilities, pumps, and piping for chlorine
dioxide feedstock chemicals
Hypochlorite cost, as savings, 20 kg/Mg
TOTAL NET COST
Annual costs
($1000)
$ 109
148
12
763
916
1,051
218
-1,020
$ 2,197
3-25
-------
TABLE 3-18. ESTIMATED TOTAL ANNUAL COST FOR MODIFYING C-E-H-E-D KRAFT
MILL BLEACH SEQUENCE TO C-E -D-E-D FOR 545 Mg/DAY MILL
(mid-1983 dollars)
1.
2.
3.
4.
5.
6.
7.
Cost items
Chloride dioxide bleach stage, installed
Chlorine dioxide generator, installed
Chlorine dioxide chemical, 7 kg/Mg
Oxygen handling and mixing equipment, installed
Oxygen added to caustic extraction stage, 5 kg/Mg
Oxygen storage tank rental
Hypochlorite cost, as savings, 25 kg/Mg
TOTAL NET COST
Annual costs
($1000)
$ 872
916
1,841
109
39
12
-1,915
$ 1 ,850
TABLE 3-19.
ESTIMATED TOTAL ANNUAL COST OF MODIFYING C-E-H-D-E-D
KRAFT PULP BLEACH SEQUENCE TO C-E-E -D-E-D FOR
545 Mg/DAY MILL (mid-1983 dollars)
Cost items
Annual costs
($1000)
1. Oxygen handling and mixing equipment, installed
2. Oxygen added to caustic extraction stage, 5 kg/Mg
3. Sodium hydroxide added, 8 kg/Mg
4. Oxygen storage tank rental
5. Hypochlorite cost, as savings, 10 kg/Mg
TOTAL NET COST
$ -
3-26
-------
annualized control costs for the eight model mills. The model mill control
costs range from a net savings of $25,000 per year (due to reduced chemical
costs) to a net cost of $2.2 million per year.
Estimated annual control costs for each existing pulp mill presently
using hypochlorite are given in Tables 3-20 through 3-24. Annualized control
costs range from a net savings of $25,000 per year to a net cost of $5.55 million
per year.
COST-EFFECTIVENESS
The cost-effectiveness of control for each existing pulp mill was computed
from estimated annual control costs and the estimated emission reductions
shown in Tables 3-6 through 3-10 and is listed for each mill in Tables 3-20
through 3-24. Table 3-25 presents a summary of control cost-effectiveness for
each subcategory. Cost-effectiveness ranges from a net savings of $1,400 per
Mg to a net cost of $417,000 per Mg.
3-27
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-------
TABLE 3-25. SUMMARY OF CHLOROFORM CONTROL COST-EFFECTIVENESS'
$1000/Mg
Subcategory
Minimum
Maximum
Median
Mean
Market Bleached Kraft
BCT Bleached Kraft
Soda and Kraft Fine Bleached
Papergrade Sulfite
Miscellaneous Integrated
Total, all categories
136.0
69.7
161.5
416.9
411.4
416.9
-0.822
-0.575
6.2
14.2
-1.4
-1.4
-0.231
27.6
70.9
62.25
88.55
64.25
24.1
28.6
74.0
130.6
102.3
85.6
Based on mid-1983 dollars.
3-34
-------
REFERENCES
1. Rehm, R.M., et al. Chloroform Materials Balance. (Draft Report).
Prepared by GCA Corporation for U.S. Environmental Protection Agency,
Office of Pesticides and Toxic Substances. Washington, DC. Contract
No. 68-02-3168. December 1982. p. 4.
2. Analysis of Volatile Halogenated Organic Compounds in Bleached Pulp Mill
Effluent. Technical Bulletin No. 298. National Council of the Paper
Industry for Air and Stream Improvement, Inc. New York, NY. August 1977.
pp. 13-14.
3. U.S. Environmental Protection Agency. Development Document for Effluent
Limitations Guidelines and Standards for the Pulp, Paper, and Paperboard
and Builders' Paper and Board Mills. EPA-440/l-80-025b. Office of Water
Regulations and Standards. Washington, DC. December 1980. p. 57.
4. Reference 3, p. 38.
5. Reference 3, p. 95.
6. The Bleaching of Pulp. Third edition. R.P. Singh, editor. Technical
, Association of the Pulp and Paper Industry, Inc. Atlanta, Georgia.
1979. p. 5.
7. Reference 3, p. 90.
8. Reference 6, p. 6
9. Reference 6, p. 306.
10. Reference 6, p. 3.
11. Letter and attachment from W. Gillespie, National Council for Air and
Stream Improvement, New York, NY to S. Duletsky, GCA Corporation.
March 11, 1983.
12. Reference 2, p. 10.
13. Reference 3, pp. 179-180.
14. Telephone conversation between S. Duletsky, GCA Corporation and M. Barker,
Technical Association of the Pulp and Paper Industry, Atlanta, GA.
March 7, 1983.
3-35
-------
15. Reference 6, p. 315.
16. Reference 6, p. 325.
17. Telephone conversation between S. Duletsky, GCA Corporation and Mr. Prough,
KAMYR Co., Glens Falls, NY. March 25, 1983.
18. Telephone conversation between S. Duletsky, GCA Corporation and B. Collins,
KAMYR Co., Glens Falls, NY. March 9, 1983.
19. Reference 6, pp. 135-141.
20. Reference 6, pp. 311-313.
21. Letter and attachments from R. Schleinkofer, Impco Division, Ingersoll-Rand
Company, Nashua, NH, to S. Duletsky, GCA Corporation, June 30, 1983.
22. Letter and attachments from W. Gillespie, NCASI, New York, NY, to
S. Duletsky, GCA Corporation, July 8, 1983.
23. Rehm, R.M., et. al. Control Options Analysis for Chloroform. (Draft Final
Report). Prepared by GCA Corporation for U.S. Environmental Protection
Agency. Office of Policy and Resource Management. Washington, DC.
EPA Contract No. 68-02-3168. May 1983. Appendix A.
3-36
-------
4. ETHYLENE DICHLORIDE PRODUCTION
INTRODUCTION
Chloroform is formed as a byproduct during the production of ethylene
dichloride (EDC). EDC is produced from ethylene and chlorine by direct
chlorination, and ethylene and hydrogen chloride (HC1) by oxychlorination.
At most production facilities, where EDC is used on-site to produce vinyl
chloride monomer (VCM), these processes are used together in what is known as
the balanced process. In the balanced process, byproduct HC1 from the cracking
of EDC to produce VCM is used in the oxychlorination process to produce about
half of the EDC required for VCM production. The remaining EDC is produced
by direct chlorination. The balanced process consists of an oxychlorination
operation, a direct chlorination operation, and product finishing and waste
treatment operation. At EDC production facilities where VCM is not produced,
EDC is typically produced by direct chlorination.
There are currently 20 facilities in the United States that produce
EDC. Table 4-1 lists the company, location, and annual production capacity
for each facility. Figure 4-1 presents plant locations. Five of these
facilities produce EDC by direct chlorination; eleven plants use the balanced
process with oxygen-based oxychlorination; three plants use the balanced
process with air-based oxychlorination process; and one plant manufactures
EDC by air-based oxychlorination only (see Tables 4-4 through 4-21). The
most recent estimate of domestic EDC production is 5,110 Gg, a preliminary
figure for 1983.2 With the total capacity cited in Table 5-1, the overall
EDC capacity utilization for 1983 is about 58 percent.
4-1
-------
TABLE 4-1. PRODUCERS OF ETHYLENE DICHLORIDE
1
Manufacturer
ARCO Chemical Co.
Borden Chemical Co.
Diamond Shamrock Corp.
Dow Chemical U.S.A.
Location
Port Arthur, TX
Geismar, LA
Deer Park, TX
Freeport, TX
Oxyster Creek, TX
Plaquemine, LA
Annual
capacity3
(x 103 Mg)
225
230
85
725
550
940
E.I. duPont de Nemours & Co., Inc.
Conoco Chems. Co. Div.
Ethyl Corp.
Formosa Plastics Corp. U.S.A.
Georgia-Pacific Corp.
The BF Goodrich Co.
BF Goodrich Chem. Group
Convent Chem. Corp. , subsid.
PPG Industries, Inc.
Shell Chemical Co.
Union Carbide Corp.
Vulcan Materials Co.
Lake Charles, LA
Baton Rouge, LA
Pasadena, TX
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA
La Porte, TX
Calvert City, KY
Convent, LA
Lake Charles, LA
Deer Park, TX
Taft, L_A-
Texas City, TX
Geismar, LA
525
320
100
250
385
750
720
450
360
1,225
635
70b
70b
160
8,775
Capacities are flexible depending on finishing capacities for vinyl chloride
and chlorinated solvents.
}Captive use only.
4-2
-------
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
ARCO Chemical Co
Borden Chemical,
Dow Chemical USA
Dow Chemical USA
Dow Chemical USA
Conoco Chemicals
Ethyl Corp., Baton
, Port Arthur, TX
Geismar, LA
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Lake Charles, LA
Rouge, LA
Ethyl Corp., Pasadena, TX
Formosa Plastics, Baton Rouge, LA
Georgia Pacific. Corp., Plaquemine
Diamond Shamrock, Deer Park, JX-
BF Goodrich, La Porte, TX
BF Goodrich, Calvert City, KY
PPG Industries, Lake Charles,
Shell Chemical Co., Deer Park
Shell Chemical Co., Norco, LA
Union Carbide Corp., Taft, LA
Union Carbide Corp., Texas City,
Vulcan Chemical, Geismar, LA
BF Goodrich/Convent, Convent, LA
Formosa Plastics, Point Comfort, TX
LA
LA
TX
(out of production)
TX
Figure 4-1. Locations of ethylene dichloride production facilities,
4-3
-------
SOURCE DESCRIPTION
The process description below is based on the balanced EDC process, used
at all but six EDC plants. Plants which use only direct chlorination or
oxychlorination have the same inputs and initial processing steps described
for those parts of the balanced process below, and have the same storage
and purification steps as the balanced process.
The balanced process consists of an oxychlorination operation, a
direct chlorination operation, and product finishing and waste treatment
operations. The raw material for the direct chlorination process are
chlorine and ethylene. Oxychlorination involves the treatment of ethylene
with oxygen and HC1. Oxygen for oxychlorination generally is added by
feeding air to the reactor, although some plants use purified oxygen as feed
material.
Basic operations that may be used in a balanced process using air for
the oxychlorination step are shown in Figure 4-2. Actual flow diagrams for
production facilities will vary. The process begins with ethylene (Stream 1)
being fed by pipeline to both the oxychlorination reactor and the direct
chlorination reactor. In the oxychlorination reactor the ethylene,
anhydrous hydrogen chloride (Stream 2), and air (Stream 3) are mixed at
molar proportions of about 2:4:1, respectively, producing 2 moles of EDC
and 2 moles of water. The reaction is carried out in the vapor phase at
200 to 315°C in either fixed-bed or fluid-bed reactor. A mixture of copper
chloride and other chlorides is used as a catalyst.
The products of reaction from the oxychlorination reactor are quenched
with water, cooled (Stream 4), and sent to a knockout drum, where EDC and
water (Stream 5) are condensed. The condensed stream enters a decanter,
where crude EDC is separated from the aqueous phase. The crude EDC (Stream 6)
is transferred to in-process storage, and the aqueous phase (Stream 7)
is recycled to the quench step. Nitrogen and other inert gases are typically
vented to an incinerator, although at some locations this stream is released to
the atmosphere (Vent A). The concentration of organics in the vent stream
is reduced by absorber and stripper columns or by a refrigerated condenser (not
shown in Figure 4-2).
4-4
-------
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In the direct-chlorination step of the balanced process, equimolar
amounts of ethylene (Stream 1) and chlorine (Stream 8) are reacted at a
temperature of 38 to 49°C and at pressures of 69 to 138 kPa. Most commercial
plants carry out the reaction in the liquid phase in the presence of a ferric
3
chloride catalyst.
Products (Stream 9) from the direct chlorination reactor are cooled
and washed with water (Stream 10) to remove dissolved hydrogen chloride
before being transferred (Stream 11) to the crude EDC storage facility.
Any inert gas fed with the ethylene or chlorine is released-to the
atmosphere from the cooler (Vent B). The waste wash water (Stream 12)
is neutralized and sent to the wastewater steam stripper along with
neutralized wastewater (Stream 13) from the oxychlorination quench area
and the wastewater (Stream 14) from the drying column. The overheads
(Stream 15) from the wastewater steam stripper, which consist of recovered
EDC, other chlorinated hydrocarbons, and water, are returned to the
process by adding them to the crude EDC (Stream 10) going to the water
wash.
Crude EDC (Stream 16) from in-process storage goes to the drying column,
where water (Stream 14) is distilled overhead and sent to the wastewater
steam stripper. The dry crude EDC (Stream 17) goes to the heads column,
which removes light ends (Stream 18) for storage and disposal or sale.
Bottoms (Stream 19) from the heads column enter the EDC finishing column,
where EDC (Stream 20) goes overhead to product storage. The tars from the
EDC finishing column (Stream 21) are taken to tar storage for disposal or
sale.3
A number of domestic EDC producers use oxygen-enriched air or purified
oxygen as the oxidant in the oxychlorination reactor. Figure 4-3 shows basic
operations that may be used in an oxygen-based oxychlorination process. For
a balanced process plant, the direct chlorination and purification steps are
the same as those shown in Figure 4-2, and, therefore, are not shown again in
Figure 4-3. Ethylene (Stream 1) is fed in large excess of the amount used in
the air oxychlorination process, that is, two to three times the amount needed
4-6
-------
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to fully consume the HC1 feed (Stream 2). Oxygen (Stream 3) is also fed to
the reactor, which may be either a fixed bed or a fluid bed. After passing
through the condensation step in the quench area, the reaction products
(Stream 4) go to a knockout drum, where the condensed crude EDC and water
(Stream 5} produced by the oxychlorination reaction are separated from the
unreacted ethylene and the inert gases (Stream 6). From the knockout drums
the crude EDC and water (Stream 5) go to a decanter, where wastewater (Stream 7)
is separated from the crude EDC (Stream 8), which goes to in-process storage
as in the air-based process. The wastewater (Stream 7) is sent to the steam
stripper for recovery of dissolved organics.
The vent gases (Stream 6) from the knockout drum go to a caustic scrubber
for removal of HC1 and carbon dioxide. The purified vent gases (Stream 9)
are then compressed and recycled (Stream 10) to the oxychlorination reactor
as part of the ethylene feed. A small amount of the vent gas (Vent A) from
the knockout drum is purged to prevent buildup of the inert gases entering
with the feed streams or formed during the reaction.
CHLOROFORM EMISSIONS AND CONTROLS
Identified sources of chloroform emissions at EDC production facilities
include the oxychlorination vent, column vents, particularly the heads columns,
v
6
and liquid waste storage. Chloroform was not detected in an emissions test
of a direct chlorination reactor vent.1
Available chloroform emission factors for these emission points in EDC
production are listed in Table 4-2. Also listed in this table are available
control techniques and associated emission factors for controlled emissions.
Because of variations in process design and age of equipment, actual emissions
vary for each plant. Other potential sources of chloroform emissions for
which insufficient information was available for the development of chloroform
emission factors in a recent EPA study include secondary emissions of chloroform
from wastewater treatment and fugitive emissions from leaks in process valves,
5
pumps, compressors, and pressure relief valves. Fugitive emissions are
expected to be low or insignificant due to absence of chloroform in some
process components and the low concentrations where it does exist.
4-8
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4-9
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Table 4-3 summarizes estimated current chloroform emissions from EDC
production facilities. Tables 4-4 through 4-21 provide derivations and
sources as well as control information and vent parameters for individual
facilities. In this analysis, it was assumed that the oxygen process and
thermal oxidation are in use at five facilities in Louisiana which are under
negotiated agreements to make these changes to air-based processes by the end
of 1984. These plants are Borden/Geismar, Conoco/Lake Charles, Ethyl/Baton
Rouge, Formosa Plastics/Baton Rouge, and Vulcan/Geismar. Lack of plant-
specific information on liquid waste disposal or storage and other potential
chloroform emission points made estimation of their emissions impossible.
The emission estimates presented here are based on average uncontrolled
emission factors of 0.35 kg/Mg for air process vents, and 0.06 for oxygen
process vents, and a thermal oxidizer control efficiency of 98 percent,
unless noted otherwise in Tables 4-4 through 4-21. Production rates were
estimated using the capacities cited in Table 4-1 assuming that each plant is
operating at the 58 percent national average capacity utilization cited
earlier. Unless noted, vent parameters are from a previous study.
Chloroform emissions from the Union Carbide facilities in Texas City,
Texas and Taft, Louisiana were assumed to be negligible. Both of these
plants produce EDC by direct chlorination for captive use with an annual
production capacity of 70,000 Mg. The plant in Texas City vents emissions
from EDC production to a flare and the controlled emissions contain no measurable
chloroform. Information on the plant in Taft was not available; however,
based on the general similarities between the two Union Carbide facilities,
no chloroform was assumed to be emitted from the Taft plant.
Available control techniques (ACT) consist of-thermal incineration at
98 percent except where higher current control efficiencies have been reported.
For plants where current control is thermal oxidation, Tables 4-4 through 4-21
contain one entry which represents both current and ACT emissions. Where
current emissions are below those achievable by ACT, both are estimated.
4-10
-------
TABLE 4-3. ESTIMATED CHLOROFORM EMISSIONS FROM ETHYLENE DICHLORIDE
PRODUCTION FACILITIES
Manufacturer
Location
Available control
Current chloroform technique
emissions (kg/yr) emissions (kg/yr)
ARCO
Borden
Diamond Shamrock
Dow
Dow
Dow
DuPont
Ethyl
Ethyl
Formosa Plastics
Formosa Plastics
Georgia Pacific
B.F. Goodrich
B.F. Goodrich
B.F. Goodrich
PPG
Shell
Vulcan
TOTAL
Port Arthur, TX
Geismar, LA
Deer Park, TX
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Lake Charles, LA
Baton Rouge, LA
Pasadena, TX
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA
LaPorte, TX
Calvert City, KY
Convent, LA
Lake Charles, LA
Deer Park, TX
Geismar, LA
\
2,600
2,800
53,600
9,000
6,800
11,600
6,500
3,900
1,160
3,100
4,730
9,200
570
^ 10,720
4,180
15,100
7,800
19,820
173,180
2,600
2,800
1,300
9,000
6,800
11,600
6,500
3,900
1,160
3,100
4,730
9,200
570
7,050
4,180
15,100
7,800
19,820
117,210
4-11
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CONCLUSIONS
Costs and cost-effectiveness figures were not calculated for EDC production
due to the high level of current control in the industry and unavailability
of plant specific data for the few less-controlled plants. As shown in
Table 5-3, available information on current controls and emissions indicates
that all but two EDC plants are currently controlled at the level considered
available control techniques (ACT) in this study. These two plants, Diamond
Shamrock/Deer Park, TX and B.F. Goodrich/Calvert City, KY, are estimated to
account for 38 percent of current national chloroform emissions from EDC
production, with the majority of these emissions due to column vents at the
Dia'mond Shamrock facility, which were assumed to be essentially uncontrolled.
Application of ACT at these plants would result in a 33 percent decrease over
the current total.
4-30
-------
REFERENCES
1. SRI International. 1984 Directory of Chemical Producers, United States
of America. Menlo Park, California. 1984.
2. U.S. International Trade Commission. Preliminary Report on U.S. Production
of Selected Synthetic Organic Chemicals—Preliminary Totals, 1983.
S.O.C. Series C/P-84-1. Washington, DC. March 15, 1984.
3. U.S. Environmental Protection Agency. Organic Chemical Manufacturing
Volume 8: Selected Processes. Report 1: Ethylene Dichloride.
EPA-450/3-80-028c. Office of Air Quality Planning and Standards.
Research Triangle Park, North Carolina. December 1980.
4. Telephone conversation between G. Gasperecz, Louisiana Air Quality
Division, Baton Rouge, LA, and M.E. Anderson, GCA/Technology Division.
August 5, 1983.
5. Anderson, M.E., and W.H. Battye. Locating and Estimating Air Emissions
from Sources of Chloroform, Final Report. U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Research Triangle
Park, NC. Contract No. 68-02-3510, Work Assignment No. 22. March 1984.
6. Telephone conversation between G. Gasperecz, Louisiana Air Quality
Division, Baton Rouge, LA, and M.E. Anderson, GCA/Technology Division.
November 18, 1982.
7. Texas Air Control Board. Emission Inventory Questionnaire for Union
Carbide Corp., Texas City, TX. 1976.
8. Texas Air Control Board. Report on Annual SIP Investigation of ARCO
Polymers, Inc. June 23, 1982.
9. Reference 3. pp. F-2 and F-3.
10. Reference 3. p. V-3.
11. Letter from J.A. DeBernardi, Conoco Chemicals to D.R. Goodwin, Emissions
Standards and Engineering Division, U.S. Environmental Protection Agency.
May 16, 1978.
12. Letter from J.A. De-Bernardi, Conoco Chemicals to G. VonBodungen, Louisiana
Department of Natural Resources concerning hydrocarbon compliance
status. July 8, 1981.
4-31
-------
13. Letter from N.E. Garland, Ethyl Corp., Baton Rouge, LA, to J.R. Farmer,
Emissions Standards and Engineering Division, U.S. Environmental Protection
Agency. March 23, 1984.
14. Texas Air Control Board. Report of Annual Compliance Investigation of
Ethyl Corporation, Pasadena, Harris County, Texas. June 26, 1979.
15. Telephone conversation between D.A. Beck, Emission Standards and Engineering
Division, U.S. Environmental Protection Agency, and Larry Peyton, Formosa
Plastics Corp. USA, Point Comfort, TX. July 10, 1984.
16. Memo from Chris Roberie, Air Quality Specialist to G. VonBodungen,
Program Administrator, Air Quality Division, Louisiana Department of
Natural Resources concerning inspection of Georgia Pacific, Rebecca
Plant. March 30, 1981.
17. Letter from W.C: Holbrook, B.F. Goodrich Co., Cleveland, OH, to J.R. Farmer,
Emissions Standards and Engineering Division, U.S. Environmental Protection
Agency. April 16, 1984.
18. Texas Air Control Board. Report of Annual Compliance Invesigation of
Shell Chemical Company, Deer Park, Harris County, Texas. November 10, 1980.
19. Letter and accompanying Emission Inventory Questionnaires from J.W. Bosky,
Vulcan Chemicals, Geismar, LA, to G. VonBodungen, Louisiana Department
of Natural Resources, Baton Rouge, LA. June 6, 1983.
20. Letter and accompanying Emission Inventory Questionnaires from J.W. Bosky,
Vulcan Chemicals, Geismar, LA, to G. VonBodungen, Louisiana Department
of Natural Resources, Baton Rouge, LA. June 28, 1983.
4-32
-------
5. CHLOROFORM PRODUCTION
INTRODUCTION
Chloroform is produced by hydrochlorination of methanol feedstock,
and further chlorination of the resulting methyl chloride intermediate
product to produce chloroform and other chloromethanes. As shown in Table 5-1,
all of the chloroform production facilities in the U.S. use this basic process.
One plant also produces chloroform by methane chlorination. These two processes
are discussed in the first section below, followed by description of available
information on chloroform emissions, emission controls and control costs.
Figure 5-1 indicates the locations of chloroform production facilities.
As indicated in Table 5-1, one of the seven chloroform production facilities
(Stauffer/Louisville, KY) is currently on standby. The total production
capacity of the seven plants is 234,000 Mg/yr, including Stauffer. The
most recent annual chloroform production figure is 159,500 Mg, a preliminary
2
total for 1983. It has been reported that DuPont plans a late-1985 completion
date for a new chloroform production unit in Corpus Christi, Texas, with
an annual production capacity of 136,400 Mg.
SOURCE DESCRIPTION
The following descriptions of chloroform production processes are based
on EPA studies which presented configurations for hypothetical typical
45 ~ -
plants. * Individual plants may vary in design and operation. Stream
numbers cited in the text refer to Figures 5-2 and 5-3.
5-1
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1. Diamond Shamrock Corp., Belle, WV
2. Dow Chemical USA, Freeport, TX
3. Dow Chemical USA, Plaquemine, LA
4. Linden Chemicals and Plastics, Inc.
5. Stauffer Chemical Co., Louisville,
6. Vulcan Materials Co., Geismar, LA
7. Vulcan Materials Co., Wichita, KS
KY
Moundsville, WV
Figure 5-1. Locations of chloroform production facilities,
5-3
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Methanol Hydrochlon nation/Methyl Chloride Chiorination Process
The major products of the methanol hydrochlorination/methyl chloride
chlorination process are chloroform, methyl chloride, and methylene
chloride. Some byproduct carbon tetrachloride is also produced.
Basic operations that may be used in the methanol hydrochlorination/methyl
chloride chlorination process are shown in Figure 5-2. Equimolar proportions
of gaseous methanol (Stream 1) and hydrogen chloride (Stream 2) are fed
to a hydrochlorination reactor maintained at a temperature of about
350°C. The hydrochlorination reaction is catalyzed by one-of a number of
catalysts, including alumina gel, cuprous or zinc chloride on activated
carbon or pumice, or phosphoric acid on activated carbon. Methanol
conversion of 95 percent is typical.
The reactor exit gas (Stream 3) is transferred to a quench tower,
where unreacted hydrogen chloride and methanol are removed by water
scrubbing. The water discharged 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 outlet liquid from the stripper (Stream 6) consists of
dilute hydrochloric acid, which is used in-house or is sent to a wastewater
treatment system.
Methyl chloride gas from the quench tower (Stream 7) is fed to the
drying tower, where it is contacted with concentrated sulfuric acid to
remove residual water. The dilute sulfuric acid effluent (Stream 8) is
sold or reprocessed.
A portion of the dried methyl chloride (Stream 9) is compressed,
cooled, and liquefied as product. The remainder (Stream 10) is fed to
the chlorination reactor along with chlorine gas (Stream 11). The
methyl chloride and chlorine react to form methylene chloride and chloroform,
along with hydrogen chloride and a small amount of carbon tetrachloride.
The product stream from the chlorination reactor is condensed and
then stripped of hydrogen chloride. The hydrogen chloride is recycled
to the methanol hydrochlorination reactor (Stream 12). The crude mixture
5-6
-------
of methylene chloride, chloroform, and carbon tetrachloride from the
stripper (Stream 13) is transferred to a storage tank and then fed to a
distillation column to extract methylene chloride. Bottoms from this
column (Stream 15) are distilled to extract chloroform. The chloroform
and methylene chloride product streams (Streams 14 and 16) are fed to
day tanks where inhibitors are added and then sent to storage and
loading facilities. Bottoms from chloroform distillation (Stream 17)
consist of crude carbon tetrachloride, which is stored for subsequent
sale or transferred to a separate carbon tetrachloride/perchloroethylene
process.
Methane Chlorination Process
In the methane chlorination process, chloroform is produced as a
coproduct with methyl chloride, methylene chloride, and carbon tetrachloride.
Methane can be- chlorinated thermally, photochemically, or catalytically,
with thermal chlorination being the most commonly used method.
Figure 5-3 presents basic operations that may be used in the methane
chlorination process. Methane (Stream 1) and chlorine (Stream 2) are
mixed and fed to a chlorination reactor, which is operated at a temperature
of about 400°C and a pressure of about 200 kPa. Gases exiting the
reactor (Stream 3) are partly condensed and then scrubbed with chilled
crude product to absorb most of the product chloromethanes from the
unreacted methane and byproduct hydrogen chloride. The unreacted methane
and byproduct hydrogen chloride from the absorber (Stream 4) are fed'
serially to a hydrogen chloride absorber, caustic scrubber, and drying
column to remove hydrogen chloride. The purified methane (Stream 5) is
recycled to the chlorination reactor. The condensed "crude chloromethane
stream (Stream 6) is fed to a stripper, where it is separated into overheads,
containing hydrogen chloride, methyl chloride, and some higher boiling
chloromethanes, and bottoms, containing methylene chloride, chloroform,
and carbon tetrachloride.
5-7
-------
Overheads from the stripper (Stream 7) are fed to a water scrubber,
where most of the hydrogen chloride is removed as weak hydrochloric acid
(Stream 8). The offgas from the water scrubber is fed to a dilute
sodium hydroxide scrubber solution to remove residual hydrogen chloride.
Water is then removed from the crude chloromethanes in a drying column.
The chloromethane mixture from the drying column (Stream 9) is
compressed, condensed, and fed to a methyl chloride distillation column.
Methyl chloride from the distillation column can be recycled back to the
chlorination reactor (Stream 10) to enhance yield of the other chloromethanes,
or condensed and then transferred to storage and loading as product
(Stream 11).
Bottoms 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 three distillation columns in series which extract methylene chloride
(Stream 15), chloroform (Stream 17), and carbon tetrachloride (Stream 19).
Condensed methylene chloride, chloroform, and carbon tetrachloride product
streams are fed to day storage tanks, where inhibitors may be added for
stabilization. The product streams are then transferred to storage and loading
facilities. Bottoms from the carbon tetrachloride distillation column are
typically incinerated.
CHLOROFORM EMISSIONS AND CONTROLS
Documented potential sources of chloroform emissions from chloroform
manufacture by the methyl chloride chlorination process include> the venting
of inert gases from the condenser following the chloroform column, in-process
and product storage, loading product chloroform, and process fugitive emission
sources such as leaks in process valves, pumps, compressors and pressure
relief valves. In the methane chlorination process, chloroform emissions
may originate from venting inert gases from the recycle methane stream, the
emergency venting of inert gases from the distillation area, in-process and
product storage, loading product chloroform, handling and disposal of process
waste liquid, and process fugitive sources.
5-8
-------
Uncontrolled Emission Factors
Tables 5-2 and 5-3 present uncontrolled emission factors for each of the
cited emission sources, from a recent EPA study. These tables include
source designations which refer to specific process locations in Figures 5-2
and 5-3. These emission factors are for hypothetical model plants, and
actual emissions will vary due to differences in process design, age of
equipment and other factors. In the current analysis, these emission factors
were used only where recently obtained plant-specific data were not available.
Where throughputs for specific types of loading operations- were available,
the following emission chloroform-specific factors based on the AP-42 loading
loss equation were used:
Truck/rail loading with submerged fill: 0.0054 Ib/gallon
Barge loading: 0.0045 Ib/gallon
Ship loading: 0.0018 Ib/gallon
Current Emissions and Controls
Table 5-4 and Figure 5-4 summarize estimated current chloroform emissions
from operating chloroform production facilities. Fugitive emissions include
process fugitive, loading, and where applicable, secondary emissions from
process waste streams. Tables 5-5 through 5-10 provide derivations and
sources of the data summarized in Table 5-4, as well as available control
information and vent parameters.
Available Control Techniques
Current emission estimates for chloroform production facilities were
assessed to determine applicability of available emission control techniques
to significant emission sources. Table 5-11 summarizes available control
techniques (ACT) resulting from this assessment. These controls apply to
storage, handling, and process fugitive emissions at most chloroform plants,
and to process emissions at the Diamond Shamrock and Linden Chemicals plants.
These control techniques and estimated efficiencies were based on EPA and
industry information on existing and feasible controls.
5-9
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TABLE 5-4. CURRENT CHLOROFORM EMISSIONS FROM CHLOROFORM
PRODUCTION FACILITIES
Chloroform emissions (kg/yr)
Plant
Diamond •
Shamrock
Dow
Dow
Linden
Stauffer
Vulcan
Vulcan
TOTAL
Location
Belle, WV
Freeport, TX
Plaquemine, TX
Moundsville, WV
Louisville, KY
Geismar, LA
Wichita, KS
Process
35,800a
20
9,400a
4,950
310
110
50,590
Storage
15,200
2,920
8,600
Fugitive
38,300
113,120
_ 15,300
21,600 ^ 30,440
16,060 26,100
72,560
136,940
47,000
270,260
Total
89,300
116,060
33,300
56,990
42,470
119,670
457,790
Includes in-process storage.
5-12
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TABLE 5-11. AVAILABLE CONTROL TECHNIQUES FOR CHLOROFORM PRODUCTION FACILITIES
Source category Control technique Estimated efficiency (%}
Column vents9 Refrigerated condensation 95
Storage Vapor recovery and -35°C ,
refrigerated condensation 95
c
Process fugitives Monthly leak detection and
repair; equipment specifications 77
Handling Vapor recovery, -35°C refrigerated - ,
condensation and leakage reduction 90
aDiamond Shamrock, Belle, WV, and Linden, Moundsville, WV.
See text for control efficiency derivations.
°For methyl chloride chlorination. Methane chlorination process efficiency
is 76 percent. From Tables 5-2 and 5-3.
5-28
-------
Process vent emissions are reported to be less than one percent of
current total plant emissions for three of the chloroform production processes.
A pressure-relief valve venting the chloroform distillation column and in-process
storage at Dow/Plaquemine, LA accounts for 23 percent of the current plant
total, or about 8 percent of total uncontrolled emissions. The
intermittent nature of this source is not amenable to available standard control
devices for volatile organics, although some process modifications may be
feasible. Thus, controls were not specified for process emissions at these
four plants.
Due to the large total process emissions reported for the Diamond
Shamrock methyl chloride chlorination process at Belle, WU, available emission
data were used to design a refrigerated condenser which would provide control
of combined process emissions. Choice of a small refrigerated condenser
was based on current use of river water condensers on these process streams.
Other options include carbon adsorption, solvent absorption, and thermal
oxidation. Carbon adsorbers and solvent absorption are considerably more
complex than a condenser, and would be hard to justify in a retrofit situation.
Thermal oxidation would require auxiliary fuel, because the principal components
of this vent stream (methylene chloride and chloroform) are nonflammable. It
also would not result in recovery of product. Based on the theoretical
correlation between vapor pressure reduction and emission control for a
properly-sized condenser, a -43°C condenser would provide an additional
95 percent control of the existing 7°C process streams at this plant. This
control requirement was based on the best available data on characteristics
of the process emissions. ' ' The available data on process emissions
at Linden Chemical in Moundsville, WV, indicate that a similar condenser could
provide similar control at that plant.
Similar condenser efficiency estimates were the basis for potential
storage and handling controls. A 95 percent control level for chloroform
storage requires a condenser at -35°C, based on a 20°C ambient temperature
and assuming proper sizing and design to achieve maximum effectiveness.
5-29
-------
Refrigerated condensation was chosen mainly because it is the principal control
currently in use for halogenated chemical storage. Refrigerated condensation is
used at six of the seven currently controlled chloroform storage facilities
cited in this chapter and Chapter 6. One fluorocarbon 22 plant (Allied/El
Segundo, CA) uses pressurized storage. Although the size of this tank is
not known, available production and emission data indicate that it is the
smallest fluorocarbon 22 plant, and that the tank is quite small relative
to those at other plants. Since pressurized storage is only a practical control
alternative for small fixed-roof tanks, it is not applicable to the larger
tanks at chloroform production plants. Refrigerated condensation can be
applied to existing fixed roof chloroform storage tanks without taking them
out of operation, a factor which may be critical for installation of controls
at the three chloroform plants which have only one main chloroform product
storage tank.
Other options for control of emissions from storage of volatile organic
compounds include: (1) rim-mounted secondary seals or fixed-roofs on
external floating roof tanks, (2) internal floating roofs on fixed roof
tanks, (3) rim-mounted secondary seals or contact internal floating roofs
for noncontact internal floating roof tanks, (4) liquid-mounted primary seals
on contact internal floating roofs, (5) rim-mounted secondary seals on
contact internal floating roofs, (6) carbon adsorption, (7) thermal oxidation,
and (8) pressure vessels. Option 1 does not apply in this case because
external floating roofs are not used for organic chemical storage (they are
generally used only on large tanks for petroleum liquids). Options 2, 3, 4,
and 5 involve various configurations of internal floating roofs. Although
floating roofs can provide control comparable to refrigerated condensers,
chloroform's ability to dissolve rubber floating roof components would be
a problem for typical floating roofs. Use of special materials may overcome
this problem, but lack of industry experience and information on potential
rubber substitutes prevent further consideration of these options. The
need to empty and clean tanks for floating roof installation could also be
a constraint at plants without available alternate storage.
5-30
-------
Carbon adsorbers (Option 6) are not known to be used for control of
emissions from storage of organic chemicals, although they can provide
comparable control. Adsorbers are likely to require significantly more
operating labor or more sophisticated instrumentation to ensure efficient
desorption cycles under fluctuating input conditions. Provision of cooling
water and steam or vacuum for regeneration may be a consideration in the
vicinity of existing tanks. Disposal of cooling water, condensate and
spent carbon are additional considerations which are not encountered with
condensers. Thermal oxidation (Option 7) is not a preferred option for
chloroform emissions alone, because chloroform is nonflammable and would
•
require auxiliary fuel or joint control of more combustible hydrocarbons for
effective control. In addition, no chloroform recovery is possible with
thermal oxidation. As stated above, pressure vessels (Option 8) are not
practical for the size of main storage tanks used at chloroform plants. Use
of pressure vessels would also require abandoning existing fixed-roof tanks
and building new pressure vessels, which would be very expensive relative
to the add-on control options discussed above.
For control of handling emissions, the principal options are refrigerated
condensers, carbon adsorbers, and thermal oxidation. As discussed for
storage controls, carbon adsorbers and thermal oxidation have significant
disadvantages relative to refrigerated condensers, so a vapor recovery system
with a -35°C refrigerated condenser was chosen as ACT. In this case, the
theoretical condenser efficiency of 95 percent was reduced to a practical
level of 90 percent due to incomplete capture of vapor recovery systems.
The fugitive control technique cited in Table 5-11 is based on monthly
inspection and repair of valves and pumps in light liquid and gas service,
and equipment specifications including rupture disks on gas safety/relief
valves, plugs and caps on open-ended lines, closed purge systems on sampling
connections and vented seal areas on compressors (flanges are not controlled).
This combination is estimated to have an overall fugitive emission control
efficiency of 76 to 77 percent for typical chloroform production facilities,
and was chosen because it was selected as best demonstrated technology (BDT)
for the new source performance standard (NSPS) for synthetic organic chemical
manufacturing fugitive emissions.
5-31
-------
A number of secondary emission points have been reported for chloroform
production, including regeneration of molecular sieves at two plants, a waste
neutralization tank and handling of spent caustic and sulfuric acid. No ACT
were developed for these emissions, due to the intermittent, highly variable
nature of molecular sieves regeneration and the minor contribution of the
other reported emissions.
Tables 5-5 through 5-10 include the application of ACT control efficiencies
to available current emission estimates, to estimate feasible emission control
levels. Existing storage controls with efficiencies of 90-percent or
greater were assumed to remain in place under ACT. In cases where available
descriptions of plant layout made it possible to identify in-process storage
or other tanks which would not be co-located with the main storage tanks,
these tanks were not controlled at the ACT level. Where data on tank types
were not available, ACT was applied to all storage emissions, which probably
overestimates the potential control. Vent parameters for ACT were based
4 5
on model plant parameters ' and assumed condenser exit temperatures. Table 5-12
summarizes ACT emissions.
CONTROL COSTS
The following estimates of costs of available control techniques (ACT) for
chloroform production facilities are based on previous EPA studies of
applicable control programs and technologies, with additional data on capital
costs and utility usage supplied by industrial vendors. All costs are for
July 1982.
Process Control Costs
As stated in the preceding section, the only 'ACT for process emissions
are refrigerated condensers which would be retrofitted to existing river water
condensers on process vents at Diamond Shamrock/Belle, WV and Linden/Moundsville,
WV. Based on available technical data for Diamond Shamrock process emissions, '
a tentative condenser design for 95 percent control of chloroform was
performed. This condenser would run at about -40°C, handle a flow of 4.4 acfm
and requires cooling capacity of about 9,000 BTU/hr. Along with 95 percent
control of a current chloroform emission rate of 7.5 kg/hr, this condenser would
also control other process vent components at about the same efficiency. These
components include 21.2 kg/hr of methylene chloride and 0.5 kg/hr of carbon
5-32
-------
TABLE 5-12. CHLOROFORM EMISSIONS FROM CHLOROFORM PRODUCTION FACILITIES
WITH AVAILABLE CONTROL TECHNIQUES
Chloroform emissions (kg/yr)
Plant
Diamond
Shamrock
Dow
Dow
Linden
Stauffer
Vulcan
Vulcan
TOTAL
Location
Belle, WV
Freeport, TX
Plaquemine, TX
Moundsville, WV
Louisville, KY
Geismar, LA
Wichita, KS
Process
l,790a
20
9,400a
250
310
110
11,880
Storage
• 6,440
770
8,600
6,590
On
16,060
3,950
42,410
Fugitive
28,050
24,560
4,050
6,100
16,600
9,930
89,290
Total
36,280
25,350
22,050
12,940
32,970
13,990
143,580
Includes in-process storage.
5-33
-------
tetrachloride. The following cost estimate considers only recovery of
chloroform, since it is the pollutant of concern in this analysis. Credit
for recovery of other components would improve the cost effectiveness of
this condenser.
Condensers with the low temperature and small cooling requirement
cited above are not standard units in a major manufacturer's line. With
18
engineering costs, a customized unit could probably be built for $15,000.
Additional allowances of 18 percent of base cost for taxes, freight and
19
instrumentation and 74 percent for installation result in an installed
capital cost of $30,800. A previous analysis for refrigerated condensers
estimated an overall annualized capital cost factor of 29 percent, which
includes maintenance labor and material (6 percent), taxes, insurance
20
and administration (5 percent) and a capital recovery factor (18 percent).
Applying this factor results in an annualized capital cost of about $8,900.
Based on electric utility usage rates provided by a manufacturer, this
21
unit would use about 5 kW/hr. Full-time operation at a cost of $0.08/kWh
would result in an annual utility bill of $3,500. Assuming an operating
20
labor requirement of about $19/hour, an annual labor cost of about $3,500
was estimated. With the emission reduction cited in Table 5-5 and 5-8, the
following estimates of net cost and cost-effectiveness were made.
Base capital cost $ 15,000
Installed capital cost 30,800
Annualized capital cost 8,900
Utilities 3,500
Operating labor 3,500
Annual cost $ 15,900
5-34
-------
Diamond Shamrock Linden
Recovery credit ($23,200) ($3.200)
Net annual cost (credit) ($7,300) $12,700
Emission reduction 34.0 Mg/yr . 4.7 Mg/yr
Cost-effectiveness (credit) ($214/Mg) $ 2,700/Mg
Process Fugitive Control Costs
Available control technique for process fugitive emissions is a program
combining monthly inspection and repair of potential emission sources
with equipment specifications for safety/relief valves, compressor seals
and sampling connections. The control costs estimated below are based
on two different model plant sizes from a recent EPA study of fugitive
emission control costs in the synthetic organic chemical manufacturing
22
industry (SOCMI). As shown in Table 5-13, the numbers of fugitive
emission sources in these SOCMI model plants are somewhat greater than the
numbers estimated to be in chloroform service in the model plants for
methyl chloride chlorination and methane chlorination, and it is known that
the number of fugitive sources varies substantially from the model plants
in several cases. For the purposes of this study, however, it was assumed
that the SOCMI model plant costs could be used directly. Table 5-14
presents the results of applying the annualized costs below to estimated
emission reduction for the plants applying ACT in Table 5-5 through 5-10. The
methyl chloride chlorination model plant costs apply to the production
facilities using the process for which ACT is specified in Tables 5-5 through
5-10 (Diamond Shamrock/Belle WV, Dow/Freeport TX, Linden/Moundsville, WV
and Vulcan/Geismar, LA). Since both processes exist-at Vulcan/Wichita KS,
the two sets of costs would be combined for a total facility control
cost there.
Methyl chloride Methane chlorination
chlorination model plant model plant
Total installed capital $30,700 $77,600
cost
Total annualized cost $18,800 $50,700
5-35
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5-37
-------
Storage Control Costs
The controlling factor in size and cost of the ACT refrigerated
condenser for chloroform storage is the displacement of vapors caused
by transfer from day tanks to bulk storage. A 200 gallon/minute pumping
24
rate was reported for the Vulcan facility at Geismar, LA. Base capital
18
cost for a condenser to handle this displacement would be about $45,000.
It is assumed that this operating rate and capital costs would apply to
storage at all four chloroform facilities to which ACT applies. The factors
for installed cost and annualized capital cost discussed under Process
Control Costs also apply here, resulting in the costs shown"in Table 5-15.
Utility and labor costs were also estimated using the same basic assumptions
and rates described for process controls. The basis for the costs in
Table 5-15 is an operating time of about 300 hours, based on the annual
transfer time which would be required for the estimated annual production
at Vulcan/Geismar. Expected emission reductions from Tables 5-5 through 5-10
were used to estimate recovery credits, net annual cost and cost-effectiveness
of control at each facility.
Handling Control Costs
Estimating costs for ACT control of handling emissions (vapor recovery
systems with refrigerated condensers) is subject to considerable uncertainty
due to lack of data on the characteristics of existing tank trucks, tank
cars, ships and barges, chemical loading facilities and on the cost of vapor
recovery systems for them. A cost of about $2,000 for retrofitting gasoline
25
tank trucks for vapor recovery has been estimated. Without adequate supporting
data, it is impossible to include these items in this analysis, and the costs
below are based on available condenser costs and available data on loading
operations. This results in a rough, worst-case estimates of control costs.
In particular, potential costs for smaller facilities may be substantially
overestimated.
One source reported a single loading rack operation rate of 200 gallons/minute,
24
at a facility with two truck-loading racks and two tank car racks. Assuming
no more than two racks loading chloroform at once, a base condenser cost of
$100,000 is estimated for tank truck and tank car loading at all facilities where
5-38
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1 g
ACT applies. The same base cost has been used for control of barge and ship
loading at Dow/Freeport, assuming that marine loading facilities are not
close enough to truck and rail loading racks to allow use.of a single
condenser. Marine loading rates may be higher than the total 400 gallons/minute
assumed for truck and rail racks, but condenser costs are not directly
proportional to loading rate, and information is not available for a more
specific estimate. Applying the installation and annualization factors
discussed under Process Control Costs results in the installed and
annualized capital costs shown below. Worst-case utility and labor costs
were also estimated using the same basic assumptions and rates described
for process controls, based on the hours required in a year for loading
of the largest plant's estimated production at 200 gallons per minute. The
total loading time estimated for Vulcan/Wichita was about 600 hours per
year. It was assumed that vapor recovery and condensation equipment would
be operated only during loading, and that labor requirements for operation
of the control system would also be equal to the estimated loading time.
Electric usage was estimated to 50 kW/hr.
Control costs
for one loading location
Base capital cost $ 100,000
Installed capital cost 205,000
Annualized capital cost 59,500
Utilities 2,400
Operating labor 11,400
Annual cost ~ $ 73,300
Emission reductions, recovery credits, and cost-effectiveness were estimated
by applying the costs above to the total handling emission reductions
for ACT in Tables 5-5 through 5-10, as shown in Table 5-16.
5-40
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5-41
-------
Basis of Control Costs
All costs are in July 1982 dollars. Costs in original references were
26
inflated to July 1982 using the Chemical Engineering plant cost index.
When estimation of capital and annual costs was necessary, cost factors cited
in available EPA cost data references were used on the assumption that they
are more applicable than more generalized cost factors from other sources.
Emission reductions and product recovery credits for estimated best
controls were based only on chloroform emissions. Other compounds would also
be controlled by process and process fugitive controls, and consideration of
recovery credits for them would reduce the net costs of these controls. The
July 1982 price for chloroform used in computing recovery credits was $682/Mg
($0.33/1b).27
Summary
Table 5-17 presents a summary of estimated costs for implementation of
ACT controls at chloroform production facilities.
COST-EFFECTIVENESS
Table 5-18 presents a summary of the estimated cost-effectiveness of the
available control techniques discussed above. This summary illustrates
the variability of ACT cost-effectiveness across plants and control types.
In some cases, relatively higher cost-effectiveness of controls is due to
some level of existing control and the correspondingly lower potential emission
reduction for ACT. For example, Dow/Freeport, TX currently controls storage
emissions at 88 percent efficiency, and ACT is credited only with the marginal
control to 95 percent. In other cases, the scale of given plants and control
costs based on model plants or other point estimates" may result in higher
cost-effectiveness for small plants and efficiencies of control for larger
plants. For example, the model plant fugitive control cost and relatively
high estimated fugitive emissions result in a substantial credit for fugitive
control at Oow/Freeport. On the average, however, it appears that control of
handling emissions is the most costly per megagram of chloroform controlled,
while process vent controls and process fugitive controls are somewhat less
expensive than storage controls.
5-42
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CONCLUSIONS
This preliminary analysis indicates that current chloroform emissions
from the six operating chloroform production facilities can be reduced from
about 458 Mg/yr to 144 Mg/yr, through the use of available control techniques
This overall 69 percent reduction is due mostly to control of process
fugitive emissions and storage emissions, which represent 43 and 30 percent
of the total potential control, respectively. Process fugitive controls are
reportedly in practice at only one plant, while storage emissions are controlled
to at least 90 percent efficiency at two plants. Control-_of handling emissions
accounts for 14 percent of potential overall control with only one plant
currently controlling product loading. Control of significant process vent
emissions at two plants account for the remaining 12 percent of potential
control. As shown in Table 5-12, about 62 percent of the 144 Mg/yr remaining
after application of ACT are fugitive emissions, principally the portion of
process fugitives not affected by ACT, and uncontrolled secondary emission
sources. In-process storage tanks not covered by ACT due to distance from
principal product storage are a large part of the remaining process and
storage emissions.
The total estimated net national cost for implementation of ACT for
all sources in the chloroform production industry would be about $525,000 per
year, almost $410,000 or 78 percent of which is for control of handling
emissions. Almost all of the remaining net control cost is divided between
process fugitive and storage controls ($51,000 and $59,000 respectively).
Net costs for individual controls vary widely between plants, depending on
controls already in place and credits for recovered chloroform. Total
estimated annual costs per plant vary from $12,300- for a plant with many
ACT controls in place (Vulcan/Geismar, LA), to $435,000 for a plant assumed
to require two handling control systems, for truck/rail and marine loading,
as well as controls on process fugitives and storage. Cost-effectiveness
of individual ACT controls were estimated to range from a credit of $420/Mg
of chloroform controlled to a cost of $13,300/Mg. Combined cost-effectiveness
of all ACT controls for specific plants ranged from $960/Mg to $5,800/Mg.
Handling control systems were the most expensive on average, at $9,100/Mg, with
storage and process fugitives at $630/Mg and $380/Mg, respectively.
5-45
-------
Process vent control was estimated at $2,700/Mg and a credit of $214/Mg for
the two plants with ACT for process vents.
It should be noted that this analysis is based on the inventory of
currently-operating plants, which does not include a Stauffer plant at
Louisville, KY, reportedly permanently closed, or the planned construction of
a large facility by DuPont in Corpus Christi, TX, by late 1985.
5-46
-------
REFERENCES
1. SRI International. 1984 Directory of Chemical Producers, United States
of America. Menlo Park, California, 1984.
2. U.S. International Trade Commission. Preliminary Report on U.S.
Production of Selected Synthetic Organic Chemicals (Including Synthetic
Plastics and Resin Materials) Preliminary Totals, 1983-. S.O.C. Series
C/P-84-1. Washington, DC. March 1984.
3. Chemical Profile: Chloroform. Chemical Marketing Reporter. Schnell
Publishing Co., New York, NY. January 31, 1983.
4. Hobbs, F.D. and C.W. Stuewe. Report 6: Chloromethanes by Methanol
Hydrochlorination and Methyl Chloride Chlorination Process. In:
Organic Chemical Manufacturing Volume 8: Selected Processes.
EPA-450/3-80-028c, U.S. Environmental Protection Agency, Research
Triangle Park, NC, December 1980.
5. Hobbs, F.D. and C.W. Stuewe. Report 5: Chloromethanes by Methane
Chlorination Process. In: Organic Chemical Manufacturing Volume 8:
Selected Processes. EPA-450/3-80-028c, U.S. Environmental Protection
Agency, Research Triangle Park, NC, December 1980.
6. Anderson, M.E., and W.H. Battye. Locating and Estimating Air Emissions
from Sources of Chloroform, Final Report. U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Research Triangle
Park, NC. Contract No. 68-02-3510, Work Assignment No. 22. March 1984.
7. Letter from M.M. Skaggs, Diamond Shamrock Corp, Pasadena, TX, to
M.G. Smith, GCA/Technology Division. August 31, 1983.
8. West Virginia Air Pollution Control Commission.. Registry of Hydrocarbon
Emissions. 1977.
9. Letter from S.L. Arnold, Dow Chemical USA, Midland, MI, to J.R. Farmer,
Emission Standards and Engineering Division, U.S. Environmental Protection
Agency. February 19, 1984.
10. Dow Chemical USA, Louisiana Division, Plaquemine Plant. Hydrocarbon
Compliance Status Report to Louisiana Air Quality Division.
November 1, 1982. Telephone conversation between M.G. Smith,
GCA/Technology Division, and G. Gasperecz, Louisiana Air Quality Division,
Baton Rouge, LA, March 16, 1983.
5-47
-------
11. Hobbs, F.D. and C.W. Stuewe. Trip Report for Dow Chemical USA,
Plaquemine, Louisiana. Prepared for U.S. Environmental Protection
Agency, Emission Standards and Engineering Division, Research Triangle
Park, North Carolina. November 17, 1977.
12. Letter from A.R. Morris, LCP Chemicals-West Virginia, Inc., Moundsville,
WV, to J.R. Farmer, Emissions Standards and Engineering Division,
U.S. Environmental Protection Agency. February 9, 1984.
13. Letters and accompanying Emission Inventory Questionnaires from
J.W. Bosky, Vulcan Chemicals, Geismar, LA, to G. VonBodungen,
Louisiana Department of Natural Resources, Baton Rouge, LA, June 6
and June 28, 1983.
14. Letter from J.M. Boyd, Vulcan Chemicals, Wichita, KS, to J.R. Farmer,
Emissions Standards and Engineering Division, U.S. Environmental
Protection Agency. February 27, 1984.
15. Letter with attachments from S.G. Lant, Diamond Shamrock, Cleveland, OH,
to D.R. Goodwin, Emissions Standards and Engineering Division,
U.S. Environmental Protection Agency concerning Belle, West Virginia
facility. April 3, 1978.
16. West Virginia Air Pollution Control Commission. Registry of Hydrocarbon
Emissions. 1977.
17. Organic Chemical Manufacturing Volume 3: Storage, Fugitive and Secondary
Sources. Report 1: Storage and Handling. EPA-450/3-80-25. U.S.
Environmental Protection Agency. Office of Air Quality Planning
and Standards, Research Triangle Park, NC. December 1980. p. IV-18, V-ll
18. Telephone conversation between M.G. Smith, GCA Corporation, and
R. Waldrop, Edwards Engineering, Pompton Plains, NJ. April 15, 1983.
19. Vatavuk, W.M. and R.B. Neveril. Part II: Factors for Estimated
Capital and Operating Costs. Chemical Engineering. November 3, 1980.
pp. 157-162.
20. Organic Chemical Manufacturing Volume 5: Adsorption, Condensation,
and Absorption Devices. U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/3-80-027. December 1980. Report 2, p. V-17.
21. Typical Electric Bills, January 1, 1980-1982. Energy Information
Administration, U.S. Department of Energy. December 1980, November 1981,
November 1982.
5-48
-------
22. VOC Fugitive Emissions in Synthetic Organic Chemicals Manufacturing
Industry—Background for Promulgated Standards. EPA-450/3-80-033b.
U.S. Environmental Protection Agency, Office of Air Quality Planning
and Standards, Research Triangle Park, NC. June 1982.
23. Reference 6, Appendix A.
24. Telephone conversation between J.W. Bosky, Vulcan Chemicals, Geismar, LA,
and M.G. Smith, GCA/Technology Division. April 11, 1983.
25. Bulk Gasoline Terminals - Background Information for Proposed Standards--
Draft EIS. U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, Research Triangle Park, North Carolina.
EPA-450/3-80-038a. December 1980.
26. Chemical Engineering, McGraw-Hill, Inc. "Economic Indicators."
November 15, 1982; November 3, 1980. Index for November 1978 taken
from citation in: R.B. Neveril, GARD, Inc., Niles IL. Capital and
Operating Costs of Selected Air Pollution Control Systems. U.S.
Environmental Protection Agency, Office of Air Quality Planning
and Standard, Research Triangle Park, NC. EPA-450/5-80-002.
December 1978.
27. Chemical Marketing Reporter. Schnell Publishing Co., New York, NY.
July 12, 1982. p. 40.
28. Letter from D. McGrade, Stauffer Chemical Co., Westport, CT, to D. Beck,
Emission Standards and Engineering Division, U.S. Environmental Protection
Agency. June 7, 1984.
5-49
-------
-------
6. FLUOROCARBON 22 PRODUCTION
INTRODUCTION
The primary use of chloroform is as a feedstock for the production of
chlorodifluoromethane, fluorocarbon 22 (CHC^). Recent estimates of the
proportion of total domestic chloroform production used in~ fluorocarbon 22
production range up to 90 percent. The principal uses of fluorocarbon 22 are
as a refrigerant (accounting for 60 to 65 percent of recent chloroform production),
and as an intermediate in production of fluoropolymers (using 20 to 30 percent
of chloroform production). A small amount of fluorocarbon 22 is also used as
1 2
an aerosol propellant. '
There are currently six facilities in the United States that produce
fluorocarbon 22 on a routine basis, and one which may operate on a non-routine
basis. These plants are listed in Table 6-1? the production locations are
shown on Figure 6-1. Published statistics on fluorocarbon 22 production are
not available. References indicate that the Allied plants in Elizabeth, NJ
and El Segundo, CA, typically produce 12,100 and 2,600 Mg/yr of fluorocarbon 22,
and that DuPont production at Louisville, KY is about 45,000 Mg/yr. '
Because data are not available on the non-routine production of fluorocarbon 22
at the DuPont Montague, MI facility, it will not be addressed further in this
report.
SOURCE DESCRIPTION
Fluorocarbon 22 is produced by the catalytic liquid-phase reaction of
anhydrous hydrogen fluoride (HF) and chloroform. Basic operations that may
be used in the production of fluorocarbon 22 are shown in Figure 6-2. Chloro-
form (Stream 1), liquid anhydrous HF (Stream 2), and chlorine (Stream 3) are
pumped from storage to the reactor, along with the recycled bottoms from the
product recovery column (Stream 15) and the HF recycle stream (Stream 9).
The reactor contains antimony pentachloride as a catalyst and is operated at
o
temperatures ranging from 0 to 200°C and pressures of 100 to 3,400 kPa.
6-1
-------
TABLE 6-1. FLUOROCARBON 22 PRODUCTION FACILITIES3'4'5
Company Location
Allied Chemical Corp. Elizabeth, NJ
El Segundo, CA
E.I. duPont de Nemours Louisville, KY
and Co., Inc.3 Montague, MI
Essex Chemical Corp.
(Racon Inc., Subsidiary) Wichita, KS
Kaiser Aluminum and
Chemical Corp. Gramercy, LA
Pennwalt Corp. Calvert City, KY
aOnly the duPont facility at Louisville routinely manufactures
fluorocarbon 22; the company's Montague plant can produce
fluorocarbon 22 on a nonroutine basis.5
6-2
-------
1.
2.
3.
4.
5.
6.
Allied Chemical Corp., El Segundo, CA
Allied Chemical Corp., Elizabeth
E.I. duPont de Nemours & Co., Inc.
Essex Chemical Corp. (Racon, Inc.,
Kaiser Aluminum and Chemical Corp.
Pennwalt Corp., Calvert City, KY
NJ
Louisville, KY
subsidiary), Wichita, KS
Gramercy, LA
Figure 6-1. Locations of fluorocarbon 22 production facilities
6-3
-------
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Vapor from the reactor (Stream 4) is fed to a distillation column, which
removes as overheads hydrogen chloride (HC1), the desired fluorocarbon
products, and some HF (Stream 6). Bottoms containing vaporized catalyst,
unconverted and underfluorinated species, and some HF (Stream 5) are
returned to the reactor. The overhead stream from the column (Stream 6)
is condensed and pumped to the HC1 recovery column.
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as a liquid. The bottoms stream from the HC1 recovery column (Stream 8)
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and a denser fluorocarbon phase. These are separated in a phase separator.
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fluorocarbons, is recycled to the reactor. The denser phase (Stream 10),
which contains the fluorocarbons plus trace amounts of HF and HC1, is
allowed to evaporate and is ducted to a caustic scrubber to neutralize
the HF and HC1. The stream is then contacted with sulfuric acid and
subsequently with activated alumina to remove water.
The neutralized and dried fluorocarbon mixture (Stream 11) is
compressed and sent to a series of two distillation columns. Overfluorinated
material, fluorocarbon 23, is removed as an overhead stream in the first
column (Stream 12) and fluorocarbon 22 is recovered as an overhead stream in
the second column (Stream 14).
There are a number of process variations in fluorocarbon production.
HF may be separated from product fluorocarbons prior to hydrogen chloride
removal. Processes may also differ at the stage at which fluorocarbon 22
is separated from fluorocarbon 23: the coproduct fluorocarbons can be
separated by distillation and then cleaned separately. Fluorocarbon 23
may be vented rather than recovered. The HC1 removal system can vary with
respect to the method of removal and the type of byproduct acid obtained.
After anhydrous HC1 has been obtained as shown in Figure 6-2, it can
be further purified and absorbed in water. Alternatively, the
condensed overhead from catalyst distillation (Stream 6), can be treated
with water to recover an aqueous solution of HC1 contaminated with HF and
6-5
-------
possibly some fluorocarbons. In this case, phase separation HF recycle
is not carried out. This latter procedure is used at many older plants
in the industry.
CHLOROFORM EMISSIONS AND CONTROLS
Identified sources of chloroform emissions at fluorocarbon 22
production facilities include losses from storage of chloroform feedstock
and process fugitive emissions from sources such as process valves, pumps,
q
compressors and pressure relief valves.
None of the three process emissions identified in Figure 6-2 is a major
source of chloroform. A vent on the hydrogen chloride recovery column
accumulator purges noncondensibles and small amounts of inert gases
entering the system with the chlorine gas. While data are not available
on the emissions from this source, potential volatile organic emissions are
expected to consist of low boiling azeotropes of highly fluorinated
ethanes and methanes formed in the fluorination reactor. Vents on the product
recovery distillation columns emit only fluorocarbons 22 and 23.
Emission Factors
Table 6-2 presents estimated emission factors for fluorocarbon 22
production facilities. In the current analysis, these factors were used
only when plant-specific data were not available.
Current Emissions and Controls
Table 6-3 summarizes estimated current chloroform emissions from
fluorocarbon 22 production facilities. Tables 6-4 through 6-9 provide
derivation and sources as well as available control ^information and vent
parameters for individual facilities. Where not available for existing
13 14
storage emissions, vent parameters were taken from previous studies. '
Plant-specific fugitive emission estimates were available only for the
two Allied plants. Since Allied/El Segundo, CA, is the smallest
fluorocarbon 22 plant, all other plants were assumed to have fugitive
emissions similar to Allied/Elizabeth, NJ.
6-6
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Available Control Techniques
Available control techniques (ACT) were assessed for storage and fugitive
emissions. For storage emissions, ACT was determined to be a refrigerated
condenser with 95 percent control efficiency. The estimated 95 percent
control of storage emissions is based on the theoretical proportionality of
emission control to vapor pressure reduction with a 20°C ambient temperature
and -35°C condenser outlet temperature. Refrigerated condensation was chosen
mainly because it is the principal control currently in use for halogenated
chemical storage. Condensers are used at six of the seven.-currently controlled
chloroform storage facilities cited in this chapter and Chapter 5. One
fluorocarbon 22 plant (Allied/El Segundo, CA) uses pressurized storage.
Although the size of this tank is not known, available production and emissions
data indicate that it is at the smallest fluorocarbon 22 plant and that the
tank is quite small relative to those at other plants. Since pressurized
storage is only a practical control alternative for small fixed-roof tanks,
it is not applicable to the larger plants. Refrigerated condensation can be
applied to existing fixed roof chloroform storage tanks without taking them
out of operation, a factor which may be critical for installation of controls
at the three fluorocarbon 22 plants which have only one chloroform storage
tanks.
Other options for control of emissions from storage of volatile organic
compounds include: (1) rim-mounted secondary seals or fixed roofs on external
floating roof tanks, (2) internal floating roofs on fixed roof tanks,
(3) rim-mounted secondary seals or contact internal floating roofs for
noncontact internal floating roof tanks, (4) liquid-mounted primary seals on
contact internal floating roofs, (5) rim-mounted secondary seals on contact
internal floating roofs, (6) carbon adsorption, (7) thermal oxidation, and
(8) pressure vessels. Option 1 does not apply to this case because external
floating roofs are not used for organic chemical storage (they are genrally
used only on large tanks for petroleum liquids). Options 2, 3, 4, and 5
involve various configurations of internal floating roofs. Although floating
roofs can provide control comparable to refrigerated condensers, chloroform's
6-15
-------
ability to dissolve rubber floating roof components would be a problem for
typical floating roofs. Use of special materials may overcome this problem,
but lack of industry experience and information on potential rubber substitutes
prevented further consideration of these options. The need to empty and
clean tanks for floating roof installation could also be a constraint at
plants without available alternative storage.
Carbon adsorbers (Option 6) are not known to be used for control of
emissions from storage of organic chemicals, although they can provide comparable
control. Installation and operation of carbon absorbers is considerably more
i
complex than for condensers. Adsorbers are likely to require significantly
more operating labor or more sophisticated instrumentation to ensure efficient
desorption cycles under fluctuating input conditions. Provision of cooling
water and steam or vacuum for regeneration may be a consideration in the
vicinity of existing tanks. Disposal of cooling water, condensate and spent
carbon are additional considerations which are not encountered with condensers.
Thermal oxidation (Option 7) is not a preferred option for chloroform emissions
alone, because chloroform is nonflammable and would require auxiliary fuel or
joint control of more combustible hydrocarbons for effective control. In
addition, no chloroform recovery is possible with thermal oxidation. As
stated above, pressure vessels (Option 8) are not practical for the size of
storage tanks used at all but the smallest fluorocarbon 22 production plant.
Use of pressure vessels would also require abandoning existing fixed-roof
tanks and building new pressure vessels, which would be very expensive relative
the add-on control options discussed above.
Fugitive chloroform emissions from fluorocarbon 22 production could
potentially be reduced by instituting a control program involving inspections,
repair and equipment specifications. These fugitive emissions are believed
to be quite small, however, estimated at 200 kg/yr or less for each plant,
and less than four percent of total potential emissions at any plant. For
this reason, ACT was not applied to process fugitive emissions.
6-16
-------
The estimated ACT storage control efficiency of 95 percent was applied
to emissions estimated for currently uncontrolled chloroform storage at
fluorocarbon 22 production facilities, including Allied/Elizabeth, NJ,
Racon/Wichita, KS, and Pennwalt/Calvert City, KY. The 95 percent control
was also applied at DuPont/Louisville, KY, where the level of existing
control is only 55 percent (See Table 6-6). ACT did not apply to
Kaiser/Gramercy, LA, because 95 percent control will shortly be installed
there. Pressurized storage at Allied/El Segundo, CA, eliminates storage
emissions entirely. Of the four plants which would install refrigerated
condensers on their storage tanks, DuPont/Louisville, KY would achieve
the greatest reduction over current chloroform emissions (about 19 Mg/yr).
Note that this reduction consists of the difference between current
55 percent control and 95 percent at ACT. Pennwalt/Calvert City, KY and
Racon/Wichita, KS would control 9.5 and 9 Mg/yr respectively; Allied/Elizabeth,
NJ would reduce emissions by about 6.8 Mg/yr. This results in a national
emission reduction of about 44.4 Mg/yr. Current emissions, controlled
emissions, and emission reductions are summarized in Table 6-3. Vent parameters
for the refrigerated condensers used in ACT for chloroform storage include
their -35°C (238°K) outlet temperature, with height and diameter (15 and
0.025 meters) taken from a previous vent parameter estimate.
CONTROL COSTS
Table 6-10 presents estimated costs of control on chloroform storage
at the four fluorocarbon 22 plants to which ACT applies. The ACT condenser
would be sized to handle the maximum expected emission rate, which would occur
when chloroform being loaded into the bulk storage tank displaces air and
vapor in the headspace. The displacement rate would be the same as the
maximum chloroform loading rate. A worst case would involve saturation
conditions in the headspace, at ambient temperatures.
The available information on production, chloroform storage and loading
rates at fluorocarbon 22 plants is summarized in Table 6-11. For control
cost estimation, it was assumed that the Pennwalt and Racon plants would have
chloroform load-in rates similar to the 5,000 gallon/hr maximum rate reported
for Allied/Elizabeth, and that loading capacities at DuPont/Louisville would
6-17
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be about four times this rate, or 20,000 gallons/hr. These assumptions were
based on the relative reported emissions for these plants. The estimated
production capacity of the DuPont plant was also considered.
Base capital costs for refrigerated condenser systems to handle the
above loading rates would be about $45,000 for 5,000 gallons/hr and $75,000
for 20,000 gallons/hr. These estimates are based on costs provided by an
equipment manufacturer for the flow rates, cooling rates and -35°C operating
temperature required to achieve 95 percent control of storage emissions.
Additional allowances of 18 percent of base cost for taxes, freight and
instrumentation and 74 percent for installation result in the installed
capital costs in Table 6-10. A previous cost analysis for refrigerated
condensers estimated an overall annualized captial cost factor of 29 percent,
which includes maintenance labor and material (5 percent), taxes, insurance
and administration (5 percent) and a capital recovery factor (18 percent).
Applying this factor results in the annualized capital costs in Table 6-10.
The condensers under consideration are air-cooled, so utilities consist
of electricity for the compressor and fan. The approximate utility costs in
18
Table 6-10 were based on an estimated $0.08/kWh electric rate, assuming
condenser operation at full capacity during loading and consumption at 15 percent
of full-capacity during idling. Loading was assumed to occur 10 percent
of the time, based on actual data for Allied/Elizabeth (902 hrs/yr). Thus
total condenser operating time was estimated at 2060 hrs/yr. The condenser
sized for 5,000 gallon/hr loading rate would consume about 1V.5 kW/hr. The
unit for the 20,000 gallon/hr loading rate would be about 20 percent more
efficient per gallon loaded, and thus would use about 37 kW/hr. Operating
labor is relatively constant regardless of condenser-size, and has been
19
estimated at 10 percent of condenser operating time. Ten percent of the
estimated operating time cited above and a labor rate of $19/hr, result in
an annual labor cost of about $3900.
Recovery credits are based on emission reductions from Table 6-3.
Recovery credits are based on the July 1982 price for chloroform, $682/Mg
($0.33/lb).20
6-20
-------
All above costs are in July 1982 dollars. Costs in original references
21
were inflated to July 1982 using the Chemical Engineering plant cost index,
except the electric utility rate for July 1982, which was projected from
1 8
available rate data.
COST-EFFECTIVENESS
Table 6-10 provides estimated cost-effectiveness of the storage controls
specified as available control techniques in the previous section. For
individual plants, these controls are estimated to cost from $2,200 to $4,100 per
megagram of chloroform controlled, with an industry-wide average of $2,800 per
megagram.
CONCLUSIONS
With 95 percent control of storage emissions at the four fluorocarbon 22
plants which do not currently have that level of control, total chloroform
emissions from this source category can be reduced from about 50 Mg/yr to
about 5.7 Mg/yr, at a total annual cost of $122,300. This annual cost
includes a chloroform recovery credit of $30,200 and a pre-recovery cost of
$152,000. Overall cost-effectiveness of available control techniques is estimated
at $2,800 per megagram.
6-21
-------
REFERENCES
1. Chemical Profile: Chloroform. Chemical Marketing Reporter. Schnell
Publishing Co., New York, NY. January 31, 1983.
2. Chemical Products Synopsis—Chloroform. Mannsville Chemical Products,
Cortland, NY. February 1981.
3. SRI International. 1984 Directory of Chemical Producers, United
States of America. Menlo Park, CA. 1984.
4. Letter from U.S. Turetsky, Allied Chemical, to D. Patrick, Strategies
and Air Standards Division, U.S. Environmental Protection Agency,
Research Triangle Park, NC. May 28, 1982.
5. Telephone conversation between D.S. Olson, E.I. duPont deNemours and
Company, Wilmington, DE, and E. Anderson, GCA/Technology Division.
November 18, 1983.
6. Telephone conversation between W.K. Whitcraft, E.I. duPont deNemours
and Company, Wilmington, DE, and M.G. Smith, GCA/Technology Division.
April 19, 1983.
7. Pitts, D.M. Report 3: Fluorocarbons (Abbreviated Report). In:
Organic Chemical Manufacturing Volume 8: Selected Processes.
EPA-450/3-8Q-028c. U.S. Environmental Protection Agency, Research
Triangle Park, NC, December 1980.
8. Dow Chemical U.S.A. Industrial Process Profiles for Environmental
Use, Chapter 16: The Fluorocarbon-Hydrogen Fluoride Industry.
EPA-600/2-77-023p, U.S. Environmental Protection Agency, Cincinnati,
OH, February 1977.
9. Anderson, M.E., and W.H. Battye. Locating and Estimating Air Emissions
from Sources of Chloroform, Final Report. U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standard, Research Triangle
Park, NC. Contract No. 68-02-3510, Work Assignment No. 22. March 1984.
10. Telephone conversation between E. Anderson, GCA/Technology Division and
McCrillus, Racon, Inc., Wichita, KS. January 13, 1983.
11. Louisiana Air Quality Division, Baton Rouge, LA. File for Kaiser
Aluminum and Chemical Corporation, Gramercy, LA. November 1982.
6-22
-------
12. Letter from R.B. McCann, Kentucky Division of Air Pollution Control,
Frankfort, KY, to R.M. Rehm, GCA/Technology Division. November 30, 1982.
13. Systems Applications, Inc. Human Exposure to Atmospheric Concentrations
of Selected Chemicals. Volume II. U.S. Environmental Protection Agency.
EPA Contract No. 68-02-3066. Office of Air Quality Planning and
Standards, Research Triangle Park, North Carolina. February 1982.
p. 8-13.
14. U.S. Environmental Protection Agency. Organic Chemical Manufacturing
Volume 8: Selected Processes. Report 6: Chloromethanes Manufactured
by Methanol Hydrochlorination and Methyl Chloride Chlorination Process.
EPA-450/3-80-028c. Office of Air Quality Planning and Standards.
Research Triangle Park, North Carolina. December 198GK p. B-l.
15. Telephone conversation between R. Waldrop, Edwards Engineering,
Pompton Plains, NJ, and M.G. Smith, GCA/Technology Division.
April 15, 1983.
16. Vatavuk, W.M. and R.B. Neveril. Part II: Factors for Estimated
Capital and Operating Costs. Chemical Engineering. November 3, 1980.
pp. 157-162.
17. Organic Chemical Manufacturing Volume 5: Adsorption, Condensation, and
Absorption Devices. U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/3-80-027. December 1980. Report 2. p. V-17.
18. Typical Electric Bills, January 1, 1980-1982. Energy Information
Administration, U.S. Department of Energy. December 1980. November 1981,
November 1982.
19. Reference 17, p. IV-3.
20. Chemical Marketing Reporter, Schnell Publishing Co., New York, NY.
July 12, 1982. p. 40.
21. Chemical Engineering, McGraw-Hill, Inc. "Economic Indicators." March 24, 1980
and November 15, 1982.
6-23
-------
7. OXYBISPHENOXARSINE/1.3-DIISOCYANATE MANUFACTURE
INTRODUCTION
Oxybisphenoxarsine (OBPA) and 1,3-diisocyanate are produced by Aerojet
General Corporation in Sacramento, California. OBPA is a fungicide that is
combined with rubber to prevent mold growth on gaskets and seals. 1,3-Diisocyanate
is an intermediate in the production of polyurethane resins. Both the OBPA
and diisocyanate processes use chloroform as a solvent. A third source of
chloroform emissions from the Aerojet facility is a deep well deaerator. All
three sources are described separately below.
OXYBISPHENOXARSINE
The Chemical Operations Division of Aerojet General Corporation is the
only producer of Oxybisphenoxarsine. For this reason, much of the information
on the production of OBPA is limited and believed to be proprietary. It is
known that chloroform acts as a carrier solvent for OBPA.
On November 29, 1982, Aerojet received a permit to construct an activated
carbon system to reduce chloroform emissions at the OBPA facility from 635 kg/day
to 30 kg/day (95 percent control). The carbon adsorption unit is a Series 500
System manufactured by VIC Manufacturing Company. Although Aerojet estimated
95 percent control and this level is used in emission estimates, preliminary
data supplied by the County of Sacramento Air Pollution Control District
[j
2
indicate the system may be achieving 98 percent control. Chloroform emissions
and stack parameters from the OBPA process are reported in Table 7-1.'
1,3-DIISOCYANATE
Like OBPA, little information is known about the Aerojet 1,3-diisocyanate
process. From other sources it is known that carbon tetrachloride can be used
as an absorbent in a scrubber which is part of a phosgene/isocyanate process
3 4
in West Virginia and Texas. ' Because little information was available on
the Aerojet process, it can be surmised that this is how chloroform is used.
7-1
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It is known that chloroform sources from 1,3-diisocyanate production
at Aerojet include the acid chloride area scrubber columns, the process
area scrubber column, the azide abatement area scrubber column, the Nash
vacuum system circulation vessels, the high vacuum still area knockout pot,
and the chloroform recycle area knockout pot. These sources are routed to
an inlet duct of the chloroform recovery system. The chloroform recovery
system is a carbon adsorber recently installed by VIC Manufacturing Company.
Emission rates and stack parameters from the 1,3-diisocyanate process are
2
reported in Table 7-1.
DEAERATION
The design purpose of a vacuum deaerator is to remove the corrosion
contributing noncondensable gases from water, namely oxygen, nitrogen,
and carbon dioxide prior to deep well injection. Because volatile organics,
such as chloroform, have a limited solubility in water, a portion of these
materials are also removed from the deaeration process. Sources of chloroform
that supply aqueous waste to the deaeration system include both the OBPA and
the diisocyanate facility.
Aerojet estimates chloroform emissions from the deep well deaeration
facility amount to 22.7 kg/day. There are no controls on this facility. Stack
2
parameters are shown in Table 7-1.
7-3
-------
REFERENCES
1. Letter from Eric P. Skelton, County of Sacramento Air Pollution Control
District to Richard Rehm, GCA/Technology Division. June 29, 1984.
2. Hill, J.A. and P.M. Painter. lO-lO'-Oxybisphenoxarsine (OBPA) Production
Facility: A Review of Its Emission Controls and Air Quality Impacts.
Aerojet General Corporation, Sacramento, Environmental Operations,
Sacramento, California. October 25, 1982. p. III-6.
3. A.D. Little, Inc. An Integrated Geographic Study of Potential Toxic
Substance Control Strategies in the Kanawha River Valley, West Virginia.
Office of Pesticides and Residual Management, U.S. Environmental Protection
Agency, Washington, DC, 1977. Appendix A, pp. 101, 102.
4. 1980 Emission Inventory Questionnaire Data Retrieval for Carbon Tetrachloride.
Abatement Requirements and Analysis Division, Texas Air Control Board,
Austin, TX, June 10, 1982.
7-4
-------
8. PHARMACEUTICAL AND VITAMIN C PRODUCTION
This chapter presents the results of a recent survey of domestic pharmaceutical
manufacturers' chloroform usage and disposal, as well as a summary of chloroform
usage and emissions at one facility producing Vitamin C.
PHARMACEUTICAL PRODUCTION
Chloroform is one of many solvents used in the manufacture of synthetic
Pharmaceuticals. Pharmaceuticals are typically made in a series of batch
operations, many of which can involve the use of solvents. These operations
include reactors, distillations, filters, extractors, centrifuges, crystallizers,
dryers and various holding tanks. Solvent emissions can occur in any of
these process steps, and can also occur from solvent storage, transfer, and
recovery systems. Solvents may be used as a reaction medium, to dissolve an
intermediate product prior to a process step, to wash an intermediate or
final product, or as a drier after a water-based production step. Except
for the Vitamin C production process described later in this chapter, no
information is available on specific locations, applications, or emission
points for chloroform use in the pharmaceutical industry.
The Pharmaceutical Manufacturer's Association conducted a survey of
2
solvent use by member companies in May 1984. The chloroform purchase,
emission and disposal statistics provided by this survey are as follows:
Annual chloroform purchase 1150 Mg
Direct air emissions 575 Mg
Sewer 150 Mg
Incineration 100 Mg
Contract haul 50 Mg
Other disposal or loss 250 Mg
8-1
-------
Respondents to this survey account for about half of the 1982 domestic sales
of ethical Pharmaceuticals, so actual chloroform usage and loss rates are
significantly higher than the responses totalled above. However, it is
believed that some surveyed manufacturers may not have responded because they
do not use the subject solvents. Thus doubling the above responses would
probably result in overestimation of true chloroform usage and losses. The
"other disposal or loss" category may include off-site solvent recovery,
deep-well injection, lab-pack disposal by outside vendors and undetermined
losses.
From these statistics, it appears that roughly 1,000 Mg/yr of chloroform
may be emitted directly to the air by pharmaceutical manufacturers, with some
significant indirect atmospheric losses from chloroform disposed of in sewers.
This total includes the emissions from the Vitaminc C production process
described in the next section. The survey cited did not provide any locations
or other company or plant-specific details.
VITAMIN C PRODUCTION
Source Description
Chloroform is used as a solvent in the manufacture of crude ascorbic
acid (Vitamin C). The starting material for ascorbic acid is dextrose, which
is hydrogenated to sorbitol, fermented, and crystallized into sorbose. The
sorbose is then slurried in a solvent reactor, followed by mixture with acid
and then neutralized. Following this the material is oxidized and dried,
forming diacetone gulosonic acid (DAG). The DAG is slurried with chloroform,
followed by a rearrangement to form crude ascorbic acid. The ascorbic acid
is filtered from the chloroform-containing mother liquor, crystallized,
o
dried, and shipped out as a final product.
Source Locations
There are two producers of Vitamin C in the U.S., Hoffman-LaRoche,
Belvidere, New Jersey, and Pfizer, Groton, Connecticut. The Hoffman-LaRoche
plant has a capacity of 30 million pounds per year, while the smaller Pfizer
4
plant has a capacity of 2 million pounds per year. The remainder of this
discussion will address only the Hoffman-LaRoche plant, since detailed information
was not gathered for the Pfizer plant.
8-2
-------
Chloroform Emissions and Controls
Potential chloroform emission sources in the Hoffman-LaRoche Vitamin C
production include: fugitive losses from process equipment and solvent
recovery equipment; vent emissions from the carbon adsorber used to control
process, recovery system and storage tank vents; an uncontrolled chloroform
storage tank; inadvertent spills of solvent or process materials; and
vaporization from wastewater and cooling water. Recent estimates for these
emissions are as follows:
Fugitive 116 Mg/yr
Carbon adsorber vent 78 Mg/yr
Storage tank 6 Mg/yr
Spills 10 Mg/yr
Wastewater/cooling water 13 Mg/yr
Total 223 Mg/yr
The current carbon adsorber is estimated to provide 78 percent control
of ducted emissions from a large number of process unit vents, the solvent
recovery unit condensers, and three of the four storage tanks. Plans exist
to continue upgrading of this adsorber, by improving post-regeneration drying
and use of a gas chromatograph for better timing of the desorption cycle. A
realistic future control level of 95 percent is projected. This would
result in carbon adsorber vent emissions of less than 20 Mg/yr, compared to
the current 78 Mg/yr cited above.
Control Costs
The initial cost of the carbon adsorber itself was $34,500 in 1978, with
additional installation costs of $500,000 in 1981, and an upgrading of the
system in 1983 for $131,000. Current annual operating costs are estimated at
$40,000 for steam, $13,500 for maintenance, and $53,500 for operating labor.
3
The value of the recovered solvents is estimated at $218,000 per year.
8-3
-------
REFERENCES
1. U.S. Environmental Protection Agency. Control of Volatile Organic Emissions
from Manufacture of Synthesized Pharmaceutical Products. EPA-450/2-78-029,
Research Triangle Park, NC, December 1978.
2. Letter from T.X. White, Pharmaceutical Manufacturers Association,
Washington, DC, to D.A. Beck, Emission Standards and Engineering
Division, U.S. Environmental Protection Agency, Research Triangle Park,
NC. June 8, 1984.
3. Letter from J.S. Kace, Hoffman-LaRoche, Nutley, NJ, to R.M. Rehm,
GCA/Technology Division. March 23, 1983.
4. SRI International. 1984 Director of Chemical Producers, United States of
America. Menlo Park, CA. 1984.
5. Letter from J.S. Kace, Hoffman-LaRoche, Nutley, NJ, to D.A. Beck,
Emission Standards and Engineering Division, U.S. Environmental
Protection Agency, Research Triangle Park, NC. June 4, 1984.
6. Memo from M.G. Smith, GCA/Technology Division, to D.A. Beck, Emission
Standards and Engineering Division, U.S. Environmental Protection Agency,
Research Triangle Park, NC. April 18, 1984.
8-4
-------
9. TRICHLOROETHYLENE PHOTODEGRADATION
SOURCE DESCRIPTION
Trichloroethylene (TCE) is a synthetic organic chemical used almost
exclusively (>90 percent) in degreasing operations. The chemical has
become pervasive in the environment due to fugitive emissions during
production, use, and disposal.
Production of trichloroethylene has been declining since the early
1970's. Production of trichlorethylene has fallen from 206,000 Mg in
1U
2
1 ?
1973 to 109,000 in 1982. ' This trend is expected to continue through
1987 with a 0 to 3 percent annual decline through the period.'
Only two sites in the U.S. manufacture trichloroethylene: Dow
Chemical in Freeport, Texas and PPG Industries in Lake Charles, Louisiana.
Releases from production are only a small part of the total released
each year.
Trichloroethylene uses include solvent degreasing, miscellaneous solvent
uses including the production of funigicides, cleaning fluids, and adhesives,
and as a chain terminator in polyvinyl chloride manufacture. Approximately
2
22 percent of all trichloroethylene manufactured is exported.
Almost all TCE production is ultimately released to the environment,
except for 6 percent which is consumed as a feedstock or destroyed by incineration,
During or following use, as much as 79 percent of production is released to
air, 14 percent to land, and 1 percent to ambient waters. Once airborne,
trichloroethylene remains in the troposphere until it reacts with hydroxyl
free radicals (-OH), the principal scavenging mechanism for trichloroethylene
and most other halogenated compounds. Decomposition products include
dichloroacetyl chloride, phosgene, carbon monoxide, chloroform, hexachlorobutene,
and hydrochloric acid. The estimated residence time for trichloroethylene
3 4
in the atmosphere ranges from 11 to 15 days. '
9-1
-------
Laboratory experiments have demonstrated the photochemical formation of
5
chloroform from trichloroethylene. In one study, synthetic mixtures of
trichloroethylene, nitrogen dioxide, water vapor, and a hydrocarbon mixture
were irradiated by a bank of fluorescent lamps designed to simulate the
intensity and spectral distribution of light prevailing in the lower troposphere.
The hydrocarbon mixture was a typical gasoline consisting of 60 percent
paraffins, 13 percent olefins, and 27 percent aromatics. Approximately
2 hours after initiation of the experiment, chloroform formation began.
After 48 hours, approximately 7 ppb of chloroform was formed (Figure 9-1).
Phosgene was measured at a level slightly lower than chloroform. Dichloroacetyl
chloride and HC1 were both measured during the experiment, but the concentration
could not be measured because of the procedures employed.
Time, hrs
Figure 9-1. Chloroform formation due to- photochemical
decomposition of trichloroethylene.
The following reaction mechanism is believed to account for the observed
formation of the products mentioned above. The mechanism involves a
chlorine-sensitized photo-oxidation of trichloroethylene. The mechanism
accounts for the products and the time lag in the experiment mentioned above.
Time is required for the initial propagation of chlorine radicals, oxygen
radicals, and other radical species. The mechanism believed to account for
the formation of chloroform from trichloroethylene is as follows:
9-2
-------
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C2HC1402 ^2C2HC
-^CHC1COC12 + Cl'
-^COC12 + CHC12-
— ^CC13- + HC1 + CO
— ^coci2 + ci-
^CHC13
As stated above, 109,000 Mg of trichloroethylene was produced in 1982.
Subtracting exports and assuming that 79 percent of trichloroethylene produced
enters the atmosphere, 67,200 Mg were released to the atmosphere. As shown
in Figure 9-1, for every ppm of trichloroethylene in the atmosphere, 7 ppb of
chloroform is formed, or of the 67,200 Mg of trichloroethylene released,
420 Mg of chloroform is formed. Secondary formation of chloroform from
trichloroethylene photodegradation is unlikely to cause significant ground
level concentrations. Maximum concentrations of trichloroethylene in urban
atmospheres have been reported to be 3.07 ppb, with average concentrations
being approximately 213 ppt. Using the ratio listed above, maximum concentrations
of chloroform in urban atmospheres due to trichloroethylene photodegradation
o
would be 21.5 ppt (105 ng/m ), while average concentrations would be 1.5 ppt
(7.3 ng/m ). This level would account for 0.77 percent of chloroform found
in urban atmospheres.
Because chloroform is formed as a secondary by-product of the hydrolysis
of trichloroethylene, direct control is not possible; The only possible
means of reducing chloroform formation would be to reduce trichloroethylene
use further by continued substitution to other halogenated solvents (e.g.
1,1,1-trichloroethane, or methylene chloride), or by use of alternate cleaning
methods.
9-3
-------
REFERENCES
1. Thomas, R., M. Byrne, et al. An Exposure and Risk Assessment for
Trichloroethylene. U.S. Environmental Protection Agency, Office of
Water Regulations and Standards, Washington, DC. EPA Contract No. 68-01-5949.
October 1981.
2. Chemical Profile: Trichloroethylene. Chemical Marketing Reporter. Schnell
Publishing Company. New York, New York. February 14, 1983.
3. Crutzen, P.A., I.S.A. Isaken, and J.R. McAfee. The impact of the
chlorocarbon industry on the ozone layer. J. Geophy. Res. 83: 345-362,
1978.
4. Derwent, R.G., and A.E.J. Eggleton. Halocarbon lifetimes and concentration
distributions calculated using a two-dimensional tropospheric model.
Atmos. Environ. J2.: 1261-1269, 1978.
5. U.S. Environmental Protection Agency. Atmospheric Freons and Halogenated
Compounds. EPA-600/3-78-108. Environmental Sciences Research Laboratory,
Research Triangle Park, North Carolina. November 1976.
6. Letter from L.T. Cupitt, U.S. EPA, Research Triangle Park, NC to M.G. Smith,
GCA/Technology Division, June 8, 1982.
9-4
-------
10. COOLING WATER
In steam electric power generators, cooling water is used to condense
steam. Cooling water is often chlorinated to prevent growth of slime-forming
organisms, which inhibit the heat exchange process, on heat-exchanger tubes.
Chloroform is formed in cooling water from the reaction between chlorine and
naturally-occurring organic compounds in the water. About 65 percent of
steam electric plants chlorinate to prevent fouling by slime-forming organisms,
The remaining plants either do not have a biofouling problem or use a control
method other than chlorine.
Two types of cooling water systems are in general use: once-through
systems and recirculating systems. Chloroform air emissions occur when
chloroform formed in cooling water evaporates to the atmosphere. Chloroform
formation and fate in cooling water is discussed below.
SOURCE DESCRIPTION
Once-Through Cooling Systems
In a once-through cooling water system, cooling water is drawn from the
water source, passed through the heat exchanger (where it absorbs heat), and
returned directly to the water source. Typically, chlorine is added to
cooling water periodically for a time period long enough to kill any organisms
growing in the heat-exchanger tubes. For example, a- large coal-fired electric
- p
plant chlorinates cooling water for 30 minutes daily. Chloroform formed in
the cooling water is discharged to the source water and evaporates.
Recirculating Cooling Systems
In a recirculating cooling water system, cooling water is withdrawn from
the water source and passed through the condensers several times before being
discharged to the receiving water. Heat is removed from the cooling water
after each pass through the condenser. Three major methods are used for
removing heat from recirculating cooling water: cooling ponds or canals;
10-1
-------
mechanical draft evaporative cooling towers; and natural draft mechanical
cooling towers. Recirculating cooling water typically is chlorinated continuously,
The evaporation of water from a recirculating cooling water system in cooling
ponds or cooling towers results in an increase in the dissolved solids concen-
tration of the water remaining in the system. Scale formation is prevented
in the system by periodically bleeding off a portion of the cooling water
(blowdown) and replacing it with fresh water which has a lower dissolved
solids concentration.
Industry Capacity
The Department of Energy listed 842 steam electric generating plants in
3
1978 with a total generating capacity of 453,000 MW. The 1982 generating
4
capacity was estimated to be 567,000 MW, an increase of 25 percent.
CHLOROFORM EMISSIONS
Once-Through Cooling Systems
The amount of chloroform formed in once-through cooling systems can^be
computed based on the volume of cooling water chlorinated and the chloroform
concentration resulting from chlorination. The water volume chlorinated can
be computed based on the cooling water flow rate in nuclear and nonnuclear
plants practicing chlorination and, because chlorination is intermittent, the
amount of time the water is chlorinated.
Approximately 60 percent of nonnuclear steam electric plants use once-
14
through cooling systems. These cooling systems used 2.0 x 10 liters of
5
water in 1978. Based on the 25 percent increase in power generating capacity
14
estimated above, an estimated 2.5 x 10 liters were used in 1982.
Because the cooling requirements at nuclear plants are about the same as
for coal-fired plants, data from a coal-fired plant can be used to estimate
the once-through cooling water volume for nuclear power plants. The average
generating capacity of U.S. nuclear power plants is 1,600 MW. The
cooling water volume at a similar-sized (1,700 MW) coal-fired plant is
Q 1
5.55 x 10 liters/day. Based on the ratio of generating capacities, a 1,600
Q
MW nuclear power plant requires 5.1 x 10 liters/day. The eleven nuclear
plant once-through systems, therefore, use approximately 2.0 x 10 liters/year
of cooling water.
10-2
-------
The total cooling water volume in once-through systems, 2.7 x 10 1/yr,
is the sum of cooling water volumes in nuclear and nonnuclear steam electric
plants. Based on the example cited above, once-through systems are estimated
2
to chlorinate daily for 0.5 hour, or 2.1 percent of the operating time.
Thus, assuming 65 percent of once-through cooling water is chlorinated 2.1 percent
12
of the time yields a total chlorinated volume of 3.7 x 10 liters per year.
Using a measured 20.5 ug/1 chloroform concentration in a once-through cooling
system as a basis, an estimated total of 75.9 Mg/year of chloroform are
o
produced in all once-through systems from chlorination. The entire amount
would evaporate to the atmosphere.
Recirculating Cooling Systems
The amount of chloroform produced in recirculating cooling systems can
be estimated by multiplying the blowdown volume of cooling systems by a
published cooling system chloroform production factor. Total chloroform
production in recirculating cooling systems has been estimated to be 4.32 x
10 kg per liter of blowdown for a continuously chlorinating cooling tower,
and 6.6 x 10" kg per liter of blowdown for a cooling tower chlorinating once
g
per week.
Recirculating cooling systems in nonnuclear steam electric plants discharged
3.2 x 1011 liters of blowdown in 1978.10 It is estimated that 4.0 x 1011 liters
were discharged in 1982, based on a 25 percent increase in generating capacity.
Nuclear power plants account for 12 percent of the power generated in the
4
United States. Assuming that nuclear power plants produce an amount of
blowdown equal to 12 percent of the nonnuclear blowdown volume, nuclear
plants discharge 4.8 x 10 1/yr of blowdown. The total blowdown volume
discharged from recirculating cooling systems, 4.5 x 10 1/yr, is the sum of
blowdown from nuclear and nonnuclear plants.
Assuming that 65 percent of recirculated cooling water is chlorinated,
2.9 x 10 liters/yr of blowdown are chlorinated. Assuming that all chlorinating
cooling towers chlorinate continuously yields an estimate of 125 Mg/yr of
chloroform produced. Assuming all chlorinating cooling towers chlorinate
intermittently yields an estimate of 191 Mg/yr of chloroform produced.
Because most plants chlorinate continuously, the amount of chloroform produced
10-3
-------
is probably best estimated by the quantity 125 Mg/yr. However, by estimating
chloroform production based on the assumption that all systems chlorinate
intermittently a reasonable range of potential chloroform emissions can be
established. Thus, an estimated 125 to 191 Mg/yr of chloroform are produced
in recirculating cooling systems. Virtually all the chloroform formed in
recirculating cooling systems evaporates to the atmosphere.
Summary of Chloroform Production
In conclusion, the amount of chloroform produced by chlorination in
once-through cooling systems and recirculating systems is calculated to be
between 197 and 263 Mg/yr. Seventy-two megagrams are discharged directly to
water (then evaporated to the air) by once-through systems, while 125 to
191 Mg/yr are emitted to the air by recirculating systems.
CHLOROFORM CONTROL METHODS
Chloroform emissions can be reduced by using a biofouling control method
other than chlorination. Alternatives to chlorination are other oxidizing
chemicals, nonoxidizing biocides, and mechanical cleaning. None of these
alternatives, however, are used widely at this time.
10-4
-------
REFERENCES
1. U.S. Environmental Protection Agency. Development Document for Effluent
Limitations Guidelines and Standards for the Steam Electric Point Source
Category. EPA-440/1-80-0295. Office of Water Regulations and Standards.
Washington, DC. September 1980. p. 66.
2. Jolley, R.L., W.R. Brungs, and R.B. Gumming. Water Chlorination:
Environmental Impacts and Health Effects. Volume 3. Ann Arbor
Science Publishers, Inc. Ann Arbor, Michigan. 1980. p. 696.
3. Reference 1, p. 33.
4. Reference 1, p. 34.
5. Reference 1, p. 62.
6. Telephone conversation between S. Duletsky, GCA Corporation and
B. Samworth, Nuclear Regulatory Commission. Washington, DC.
November 29, 1982.
7. Telephone conversation between S. Duletsky, GCA Corporation and
G. Ogle, TRW. November 17, 1982.
8. Reference 2, p. 702.
9. Reference 2, pp. 700-701. .
10. Reference 1, p. 67.
10-5
-------
-------
11. DRINKING WATER
This chapter discusses the importance of drinking water treatment as a
source of chloroform air emissions and the potential effectiveness of chloro-
form formation control techniques. A brief description of-water treatment
processes is presented, followed by a discussion of chloroform formation,
emissions potential, chloroform control techniques, and the cost-effectiveness
of control techniques.
SOURCE DESCRIPTION
The purpose of drinking water treatment is to make the water safe and
attractive for the consumer by removing contaminants in the raw water. The
principal contaminants of concern in most water sources are pathogenic
bacteria, turbidity and suspended materials, color, tastes and odor, trace
organic compounds, and hardness. Figure 11-1 shows schematic flowsheets for
two typical water treatment plants. Sedimentation, preceded by alum addition,
mixing, and flocculation, removes a large percentage of suspended materials
including bacteria, sediment, and turbidity. Chlorine addition oxidizes
certain chemicals and kills pathogenic bacteria. The sand filters remove
unsettled floe particles and suspended bacteria. Where needed, carbon
powder can remove certain amounts of trace organic compounds.
CHLOROFORM FORMATION
Chloroform is formed during chlorination of drinking water by a complex
reaction mechanism between chlorine and organic precursors in raw water. The
organic precursors are natural aquatic humic substances such as humic and
2
fulvic acids. Major factors influencing this reaction are the amount and
type of precursor material present in raw water, temperature, pH, and
chlorine dose. These factors influence both the chloroform formation rate
and the terminal chloroform concentration. The reaction rate between chlorine
and precursor material is important because the reaction can continue to form
11-1
-------
Source
Source
To storage reservoir
or distribution system
Note: The small unlabeled
squares represent
chemical feeding
devices
Chlorine
Carbon
dioxide
•| | Chlorine
To storage
reservoir or distribution
system
(a) Conventional
for most surface
waters requiring
complete treatment
(b) For waters requiring
complete treatment
including softening
Figure 11-1. Schematic of typical water treatment plants.'
11-2
-------
chloroform in water distribution mains long after the water has left the
treatment plant. Data show that as much as 87 percent of the chloroform
formation potential can remain in the water following treatment. The
time-dependent nature of the chloroform formation reaction is an important
consideration in evaluating chloroform air emissions and control techniques.
The extent and severity of chloroform in the Nation's drinking water was
shown by two surveys conducted by EPA: The National Organics Reconnaissance
Survey (NORS) made in 1975 and the National Organics Monitoring Survey (NOMS)
made in 1977. The NORS analyzed raw and treated water samples from 80
U.S. cities to determine the organic compound content of the water, including
chloroform concentrations. The samples were collected and iced for shipment,
but not dechlorinated. Thus, the NORS chloroform concentrations in finished
drinking water are minima for those locations. The chloroform concentrations
in raw water samples ranged from zero to one yg/1. The NOMS analyzed
drinking water in 113 U.S. cities, including many of the same cities sampled
in the NORS. Both surveys were done prior to the establishment of a maximum
contaminant level (MCL) for trihalomethanes, and thus represent the level of
contamination generally present before controls. The results of the NORS and
NOMS and the 1980 population of the cities where samples were taken are
presented in Table 11-1. As shown by the table, chloroform concentrations
range from "not detected" to 311 yg/1. Both groundwater and surface water
sources were surveyed.
CHLOROFORM EMISSIONS
Chloroform Emissions Potential
Chloroform air emissions result when chloroform-in water is transferred
to air by evaporation. An experiment has shown that the concentration of
o
chloroform in a cup of stirred water decreased by one-half every 20 minutes.
Chloroform formed in drinking water potentially can be emitted at points
where the water system is open to the air, such as at the water treatment
plant, in open storage reservoirs for treated water, at the consumer's tap,
and in the sewerage system. Because the transfer rate of chloroform from
water to air is dependent on water depth, chloroform transfer to air in water
treatment unit processes would be much slower than in the experimental result
11-3
-------
TABLE 11-1. CHLOROFORM CONCENTRATION AND POPULATION FOR 137 CITIES
City
Albuquerque, NM
Amarillo, TX
Annandale, VA
Atlanta, GA
Baltimore, MO
Baton Rouge, LA
Bill ings, MT
Birmingham, AL
Bismark, NO
Boise, ID
Boston, MA
Brownsville, TX
Buffalo, NY
Burlington, VT
Camden, AR
Cape Girardeau, MO
Casper, WY
Cheyenne, WY
Charleston, SC
Charlotte, NC
Chattanooga, TN
Chicago, IL
Cincinnati , OH
Clarinda, I A
Cleveland, OH
Clinton, IL
Coalinga, CA
Columbus, OH
Concord, CA
Corvallis, OR
Dallas, TX
Davenport, IA
Dayton, OH
Denver, CO
Des Moines, I A
Detroit, MI
Dos Pal os, CA
Douglas, AK
Duluth, MN
Elizabeth, NJ
Erie, PA
Eugene, OR
Fort Wayne, IN
Fort Worth, TX
Fresno, CA
Grand Forks, NO
Grand Rapids, MI
Greenville, MS
Hackensack, NJ
Hagerstown, MD
Hartford, CT
Hopewell , VA
Houma , LA
Houston, TX
Huntington, WV
NOMS,
ug/1
NO
7.6
79
33
41
3
4
28
56
8
3.4
10 ,
3.5a
63
12
31
35
81
171
36
37
14
—
—
12
.._
--
208
16
NO
18
63
4
15
NO
9
..
--
7
27
18
19
62
3
NO
._
48
NO
44
40
13
—
91
123
7.2
NORS,
ug/1
0.4
—
67
36
32
__
—
—
—
—
4
12
10
—
40
116
—
—
195
—
30
15
45
48
18
4
16
134
31
26
18
88
8
14
—
1?
51
40
—
—
_.
—
—
..
—
3
—
17
—
—
_..
6
134
—
23
Average,
ug/1
0.2
7.6
73
34.5
36.5
3
4
28
56
8
3.7
11
6.8
63
26
73.5
35
81
183
36
33.5
14.5
45
48
15
4
16
171
23.5
13
18
75.5
6
14.5
ND
10.5
61
40
7
27
18
19
62
3- "
ND -
3
48
8.5
44
40
13
6
112.5
123
15.1
Population,
19SO
331,767
149,230
49,524
425,022
786,775
219,419
66,798
284,413
4-5,485
102,451
562,994
84,997
357,870
37,712
15,356
34,361
51,016
47,283
69,510
314,447
169,565
3,005,072
385,457
5,458
573,822
8,014
6,593
554,871
103,255
40,980
904,078
103,264
203,371
492,365
191,003
1,203,339
3,123
19,528
92,811
106,201
119,123
105,52*
172,196
385,164
213,202
43,765
181,843
40,513
35,039
34,132
136,392
23,397
32,602
1,595,138
63,634
CONTINUED
11-4
-------
TABLE 11-1. (CONTINUED)
City
Huron, SD
Idaho Falls, ID
Illwaco, WA
Indianapolis, IN
Jackson, MS
Jacksonville, FL
Jersey City, NJ
Kansas City, MO
Las Vegas, NV
Lawrence, MA
Lincoln, NO
Little Falls, NJ
Little Rock, AR
Logansport, LA
Los Angeles, CA
Louisville, KY
Madison, MI
Manchester, NH
Melbourne, FL
Memphis, TN
Miami , FL
Milwaukee, WI
Monroe, LA
Montgomery, AL
Mount demons, MI
Nashville, TN
Newark, DE
New Haven, CT
Newport, RI
New York, NY
Norfolk, VA
Oakland, CA
Oklahoma City, OK
Omaha, NB
Oshkosh, WI
Ottumwa, IA
Philadephia, PA
Phoenix, AZ
Pi qua, OH
Pittsburgh, PA
Portland, ME
Portland, OR
Poughkeepsie, NY
Providence, RI
Provo, UT
Pueblo, CO
Rhinebeck, NY
Richmond, VA
Rockford, IL
Rome, GA
Sacramento, CA
Salt Lake City, UT
San Antonio, TX
San Oiego, CA
San Francisco, CA
NOMS,
ug/l
193
--
174b
36b
267
9
42
29
22
—
5
64
71a .
—
32
67
NO
61
271
4
„
8.8
46
55
18
8
--
30
74
—
70
31
200
42
—
„
—
127
—
19
4.4
7
50
5
19
12
—
17
ND
65
5.6
20
ND
35
76
NORS,
u9/l
309
2
167
31
—
9
—
24
—
91
4
59
'
28
32
..
—
—
0.9
311
9
--
f
8.5C
16
0.5
—
103
22
__
44
—
—
26
0.9
86
9
131
8
—
—
—
—
2
8
—
—
—
—
20
0.2
52
41
Average,
ug/l
251
2
' 169.5
33.5
267
9
42
26.5
22
91
4.5
61.5
71
28
32
67
ND
61
271
2.5
311
. 8.9
46
55
11.7
12
0.5
30
88.5
22
70
37.4
200
42
26
0.9
86
68
131
13.5
4.4
7
50 -
5
19
7
8
17
NO
65
5.6
20
0.1
43.5
58.5
Population,
1930
13,000
39,590
604
700,807
202,895
540,920
223,532
448,159
164,674
63,175
656
11,496
158,461
1,565
2,966,850
298,451
170,616
90,936
46,536
646,356
346,865
636,212
57,597
177,857
18,806
455,651
25,247
126,109
29,259
7,071,639
266,979
339,337
403,213
314,255
49,620
27,381
1,688,210
789,704
20,480
423,938
61,572
366,383
29,757
155,804
74,108
101,686
2,542
219,214
139,712
29,654
275,741
163,033
785,880
875,538
678,974
CONTINUED
11-5
-------
TABLE 11-1. (CONTINUED)
City
San Juan, PR
Sante Fe, NM
Seattle, WA
Sioux Falls. SD
Spokane, WA
Springfield, MA
St. Croix, VI
St. Louis, MO
St. Paul , MN
Strasburg, PA
Syracuse, NY
Tacottia , WA
Tampa , FL
Toledo, OH
Toms River, NJ
Topeka, KS
Tucson, AZ
Tulsa, OK
Washington, DC
Waterbury, CT
Waterford Township, NY
Wheeling, WV
Whiting, IN
Wichita, KS
Wilmington-Stanton, DE
Youngstown, OH
Yuma, AZ
NOMS
ug/l
..
60
—
41
NO
18
62
8.1
8.6
—
8.6
1.5
109
20
—
118
—
20
53
77
48
70
1.2a
6.1
18
„
27
NORS,
ug/l
47
—
15
--
„
—
55
..
ND
—
—
—
0.6
88
0.2
—
41
93
72
—
0.5
23
80
•-
Average,
ug/l
47
60
15
41
NO
18
62
31.6
8.6
NO
8.6
1.5
109
20
0.6
103
0.2
20
47
85
48
71
1.2
3.3
20.5
80
27
Population,
1980
..
48,953
493,846
81,343
171,300
152,319
—
453,035
270,230
1,999
170,105
158,501
271,523
354,635
7,465
115,266
330,537
360,919
638,333
103,266
2,405
43,070
5,630
279,272
75,690
115,436
42,433
Phase II sample.
Phase III sample.
cAverage of 2 samples.
11-6
-------
cited above. Consumer uses other than drinking, such as washing, watering,
cooking, bathing, and industrial processes, subjects water to conditions such
as aeration, agitation, boiling, stirring, sprinkling, and periods of
quiescence that, according to results of experiments, promote chloroform
evaporation. '
As shown by Figure 11-2, chloroform is formed over a period of time from
the reaction of chlorine with organic precursors in the water. Hence, the
chloroform formation potential of chlorinated water is not reached for
several days after chlorine addition. Because typical water treatment takes
less than 10 hours (from alum mix to final disinfection), in many cases the
majority of chloroform in tap water will form in the distribution system
after treatment. Considering the chloroform water-to-air transfer rate and
the time-dependence of the chloroform formation reaction, the potential for
chloroform air emissions is greatest after water leaves the treatment plant.
Most chloroform air emissions from drinking water, therefore, probably result
from consumer use of water in the area served by the distribution system.
Chloroform Emissions Estimates
National Emissions Estimates--
The chloroform concentrations from different U.S. cities shown in
Table 11-1 indicate that the chloroform formation potential of source waters
varies widely across the country. Chloroform produced in drinking water can
be estimated by averaging the concentrations measured in the NORS and NOMS,
then multiplying the average chloroform concentration by the quantity of
water chlorinated in the U.S. annually. The volume of water treated in each
city was estimated by multiplying the population by the estimated water
consumption of 587 liters per capita per day (155 gallons per capita per
day). If a city was sampled in both NORS and NOMS, the data were averaged.
The amount of chloroform generated in each of the 137 cities sampled was
divided by the total amount of water treated to give a weighted average of
41 pg/1 of chloroform. The national quantity of water chlorinated was
estimated by multiplying the population served by primary water supplies
(214,000,000) by the estimated per capita consumption, yielding an estimated
4.6 x 10 liters per year chlorinated drinking water. Multiplying the
11-7
-------
en
tO
O)
(J
O
O
Untreated Ohio
River Water
Coagulated and
Settled Water
Dual Media
Filtered Water
40 80 120
Reaction time, hr.
160
Figure 11-2. Chloroform formation potential in raw and treated water.11
11-8
-------
national average chloroform concentration of 41 yg/1 by the national quantity
of chlorinated drinking water yields 1,900 Mg/yr chloroform produced from
chlorination. Discounting the relatively small amount of tap water ingested,
almost all of the chloroform produced evaporates to the atmosphere.
Model Plant Emissions Estimates--
The Office of Drinking Water has developed six different-sized model water
treatment plants for the purpose of estimating chloroform control costs.
These model plants were developed to cover the range of treatment plant sizes
serving greater than 10,000 people. Treatment plant capacities, average
water production, and the estimated average population served by each system
size are presented in Table 11-2. The model plants were used to estimate the
quantity of chloroform produced annually in different-sized treatment plants
at various concentration levels. The quantities are presented for a range of
concentrations because chloroform formation varies considerably between U.S.
water treatment plants. The annual chloroform produced from chlorination in
each system size at concentrations between 10 yg/1 and 100 yg/1 is presented
in Table 11-3. The quantities produced range from 36.5 kg/yr to 35,478 kg/yr.
CHLOROFORM CONTROL METHODS
Chloroform in drinking water is presently regulated by the National
Interim Primary Drinking Water Regulations; Trihalomethanes (40 CFR Part 142).
The rule establishes a maximum total trihalomethane (TTHM) contaminant level
of 0.10 mg/1 for all public water systems serving more than 10,000 persons
and specifies what treatment methods a system may be required to install or
use to comply with the TTHM MCL. While trihalomethanes in drinking water
also include bromoform, dibromochloromethane, and bromodichloromethane,
chloroform is the predominant species.
The TTHM rule identifies two categories of control methods: (1) those
technologies or treatment techniques determined to be "generally available",
taking costs into consideration; and (2) those technologies or treatment
techniques not determined to be "generally available", but which may be
available to some systems. The control methods identified in the TTHM rule
are presented below as potential chloroform controls.
11-9
-------
TABLE 11-2. MODEL WATER PLANTS AND AVERAGE POPULATION SERVED12
Plant
capacity,
105l/d
16
35
69
102
286
1,362
Average wateg
production, 10 1/d
10
22
43
64
190
972
Average
population
served9
17,035
37,480
73,254
109,029
323,680
1,655,877
Based on average per capita consumption of 587 liters/day.
TABLE 11-3. ANNUAL CHLOROFORM PRODUCTION IN MODEL PLANTS
AT VARIOUS CONCENTRATIONS
System
average
water
production,
106l/d
10
22
43
64
190
972
Annual chloroform production at given concentration (kg)
10 yg/1
36.5
80.3
157
233.6
693.5
3,547.8
20 yg/1
73
160.6
314
467.2
1,387
7,095.6
50 yg/1
182.5
- - 401.5
784.8
1,168
3,467.5
17,739
100 yg/1
365
803
1,569.6
2,336
6,935
35,478
11-10
-------
Effective control techniques for limiting chloroform in drinking water
follow three approaches: precursor removal prior to chlorination; chloroform
removal following chlorination; and use of a disinfectant that does not react
with precursors to form chloroform.
EPA has identified the best technologies, treatment techniques and other
means generally available, taking costs into consideration, that can be used
by community water systems for controlling total trihalomethanes, including
13
chloroform. The five techniques listed by EPA as being "generally available"
(also called Group I techniques) are: use of chloramines as an alternate or
supplemental disinfectant or oxidant; use of chlorine dioxide as an alternate
or supplemental disinfectant or oxidant; improving existing clarification for
precursor removal; moving the point of chlorination to reduce chloroform
formation and, where necessary, replacing chlorine used as a pre-oxidant with
chloramines, chlorine dioxide, or potassium permanganate; and the use of
powdered activated carbon (PAC) for chloroform precursor or chloroform
reduction seasonally or intermittently at dosages not to exceed 10 mg/1 on
an average annual basis.
In addition, EPA has identified five other methods not considered
"generally available" (also called Group II methods) that must be studied for
technical and economic feasibility for TTHM reduction in the event Group I
methods are not effective in reducing TTHMs sufficiently in a particular
water system. These five Group II methods are: introduction of off-line
water storage; aeration for reduction of chloroform; introduction of clarification;
consideration of alternate sources of raw water; and use of ozone as an
alternate or supplemental disinfectant or oxidant. Of these, only aeration
does not reduce chloroform production; rather, aeration transfers chloroform
from water to air. Thus, aeration is not an air emissions control technique.
Generally Available Control Methods
Use of Chloramines--
Chloramines, which have been widely used for many years in the United
States as a drinking water disinfectant, do not react with organic precursor
14
material to form chloroform. Several cities in the U.S. have already
reduced chloroform in drinking water by using chloramines. ' Chloramines
are produced in treatment plant water from the reaction of free chlorine and
11-11
-------
ammonia. In chlorine-ammonia treatment for primary disinfection, chlorine
and ammonia are added to the water simultaneously or in succession typically
at a 4:1 chlorine to ammonia ratio. Although the reaction to form chloramines
occurs in hundredths of a second at high temperatures and optimum pH (8.3),
it proceeds at much slower rates at lower temperatures and other pH values.
If ammonia addition is delayed, or if the reaction between free chlorine and
ammonia proceeds slowly, free chlorine could be present for several minutes
or even several hours.
Several cities have reduced chloroform concentrations by using chloramines.
The Louisville Water Company reduced the total trihalomethane (mostly chloroform)
concentration by adding ammonia to drinking water 10 minutes after adding
chlorine. The trihalomethane concentration was reduced from 150 yg/1 to
15 yg/1.15
Breakpoint chlorination, the practice of adding chlorine until all
natural nitrogen compounds in the water have formed combined chlorine, was
replaced by chlorine and ammonia addition following lime softening at a
treatment plant in Miami, Florida. As a result, the chloroform concentration
in finished water decreased from an average of over 100 yg/1 to an average of
approximately 10 yg/1. Moreover, the persistence of the chloramine
residual has eliminated the need for chlorine booster stations.
As 'shown by these utilities, the use of chloramines can significantly
reduce chloroform levels in treated water. Reductions of 90 percent and
controlled chloroform concentrations of 10 yg/1 are possible.
Use of Chlorine Dioxide --
Laboratory studies and use in water treatment plants show that chlorine
dioxide will disinfect without forming chloroform. Several plants in the
United States presently use chlorine dioxide for taste and odor control,
disinfection, oxidation of organics, and removal of iron, manganese and
18
color. Chlorine dioxide is an excellent biocide with an ability to
inactivate bacteria and viruses at a rate close to that of free chlorine.
Chlorine dioxide equipment can be retrofitted into water treatment
plants. Existing chlorination equipment can be used as standby. Because
chlorine dioxide is unstable, it must be generated and used on-site. Reactor
vessels are available from U.S.' manufacturers, but the simplicity of design
11-12
-------
18
has encouraged several plants to fabricate their own. Small amounts of
chlorine are carried over in chlorine dioxide production and form free chlorine
in the water. However, a study has shown that even when the free chlorine
concentration is half that of chlorine dioxide, chloroform formation is
19
reduced by 90 percent.
Improved Existing Clarification --
Improved clarification can often lower chloroform concentrations in
treated water by removing a larger fraction of organic precursor material.
In conventional clarification, coagulants such as iron salts and aluminum
sulfate (alum), calcium hydroxide (if softening is also a goal), and polymers
are used in different types of water treatment plants to remove color and
20
turbidity from raw water. A typical clarification process involves
coagulant addition and mixing, flocculation, and sedimentation. While
coagulation is most often considered a treatment technique for turbidity
reduction, the process plays an important part in removing organics, including
chloroform precursors such as humic and fulvic acids. This role occurs both
because some organic materials are absorbed on suspended particles (turbidity)
and because direct interactions of the natural humic materials (usually
20
recognized as color) take place with the coagulants themselves. The
American Water Works Association Research Committee on Coagulation has
concluded that both iron salts and alum are effective in removing humic and
fulvic acids from water, and that cationic polymers that interact with
21
anionic humates can be useful as coagulants for organics removal. Thus,
improved clarification could be expected to lower chloroform concentrations
in treated water by removing a larger fraction of chloroform precursors.
Because the organic content of raw water can vary greatly between
sources, any change in coagulant dose or type or in water pH for the purpose
of improving clarification precursor removal should be tested for
source-specific removal efficiency. The degree of improvement in clarification
possible in a treatment plant depends on the level of treatment already
practiced in the clarification process. Some water treatment plants may
already be operating the coagulation-sedimentation process near a level of
22
maximum organics removal while others may not.
11-13
-------
Moving the Point of Chlorination—
Moving the chlorination point in a treatment plant to control chloroform
is a technique closely associated with clarification. This technique is
applicable to water treatment plants that chlorinate raw water (prechlorination)
or gravity-settled water before it is treated with coagulant and clarified by
sedimentation. As described above, raw water often contains certain amounts
of organic chloroform precursor materials that can be removed by gravity
settling or coagulation and sedimentation. If chlorine is added before
gravity settling or coagulation and sedimentation, it reacts with the
precursors to form chloroform before the precursors can be removed. Because
gravity settling and coagulation-sedimentation take a relatively large amount
of time (compared to other water treatment unit processes), prechlorination
23
allows considerable time for chloroform formation. Thus, in many cases,
moving chlorination to a point after coagulation and sedimentation reduces
the amount of precursor material that the chlorine can react with, and
consequently reduces the amounts of chloroform produced in the water.
Moving the chlorination point has been ineffective in reducing chloroform
in some water treatment plants and quite effective in others (assumed from a
reduction of total trihalomethanes). The potential effectiveness of moving
the chlorination point can be determined by measuring the removal of precursors
at different points in the treatment train. This technique best reduces
chloroform concentrations if a high percentage of chloroform precursors are
settled out during clarification.
Use of Powdered Activated Carbon--
Powdered activated carbon (PAC) can be used to remove both chloroform
and chloroform precursors from water through adsorption. According to one
study on Ohio River water, about 77 mg/1 PAC is needed to lower chloroform
25
formation potential from 200 yg/1 to 100 yg/1. Because the use of such
high dosages is likely to cause sludge problems as well as be prohibitively
expensive, the TTHM drinking water rule recommends limiting PAC use to an
annual average of 10 mg/1. In some treatment plants where high chloroform
concentrations are experienced seasonally, intermittent high dosages of PAC
may sufficiently reduce peak chloroform levels without exceeding the 10 mg/1
annual average.
11-14
-------
Additional Control Methods Not Considered Generally Available
In addition to the five Group I control methods described above as
"generally available", EPA has identified five Group II control methods that
must be considered in the event that none of the Group I control techniques
reduces trihalomethane concentrations sufficiently. The five Group II
methods are described briefly below.
Off-line Water Storage—
Off-line water storage in a reservoir before coagulation, flocculation,
and sedimentation has been practiced by some utilities for many years. The
purpose of this treatment is to provide an extended period of time for solids
to settle out, thereby reducing the load on the treatment process, mitigating
extreme changes in water quality from stormwater runoff, and providing a
26
source of water during intermittent pollution episodes.
Aeration for Chloroform Removal —
Aeration has long been used in drinking water treatment to reduce taste
and odors, remove carbon dioxide, and oxidize iron and manganese for subsequent
removal. While aeration may be appropriate and effective for controlling
chloroform as a drinking water contaminant in some situations, it is not an
air emissions control technique.
Introduction of Clarification—
Many treatment plants currently treat their water without sedimentation
or filtration. The addition of either of these clarification processes might
remove a substantial fraction of chloroform precursors, and would also contribute
•
to the removal of pathogens and to more effective disinfection.
Alternate Source of Raw Water--
Some utilities may have access to other sources of raw water that are low
in precursor concentrations. The use of a new water source may result in
overall water treatment savings as well as a reduction in chloroform levels.
The technical and economic feasibility of an alternate water source must
be determined for each site. Costs for changing source water can be quite
high and vary widely.
11-15
-------
Use of Ozone--
Ozone can be used in water treatment as an alternate or supplemental
disinfectant or oxidant. Ozone is an efficient disinfectant that does not
form chloroform. It is widely used for disinfection in Europe, Canada, and
27
the Soviet Union. Communities in the United States which have added ozone
to their water treatment have had little difficulty in obtaining the necessary
28
guidance, equipment, and service help. Pilot-scale ozonation systems and
maintenance service contracts can be obtained from manufacturers.
The disadvantages of ozone are its higher cost than chlorine, lack of
sufficient residual protection, and its potential for forming organic byproducts
29
with unknown health risks.
A typical ozone installation utilizes a dosage of 3 mg/1 with a detention
time of 10 minutes, from an ozone generator with a capacity to produce 4.5 mg/1.
CHLOROFORM CONTROL COSTS
The estimated costs of applying Group I chloroform control methods to
different sizes of water treatment plants are discussed and presented below.
Capital costs, operating costs, and design criteria are presented for each
Group I chloroform control method applied to the six model treatment plant
sizes presented in Table 11-3.
Use of Chloramines
For the purpose of estimating costs, the design criteria for using
chloramines are: addition of ammonia to chlorinated water at a 4:1 chlorine
to ammonia ratio to produce chloramines; an average combined chlorine residual
of 3 mg/1; use of existing chlorine feed equipment*and addition to ammonia
feed and storage equipment; and use of either aqueous or anhydrous ammonia.
The total annualized costs for this method, presented in Table 11-4, range
from $8,000 for the smallest system to $99,000 for the largest system.
Use of Chlorine Dioxide
The design criteria for estimating the costs of using chlorine dioxide
are: chlorine dioxide at a dose of 1 mg/1 would replace chlorine as the
disinfectant; a reaction vessel would be used to combine one part chlorine
with one part sodium chlorite; and existing chlorination equipment would be
11-16
-------
TABLE 11-4. TOTAL ANNUALIZED COST OF CONTROLLING CHLOROFORM BY USING
CHLORAMINES31
Plant
capacity,
106 I/day
16
35
69
102
286
1,362
Average
water
production,
106 I/day
10
22
43
64
190
972
Average
capital
cost,
$1,000
28
36
60
70
99
208
Annualized
capital
cost,
$l,000a
3
4
7
8
12
25
Average
annual
operating
cost, $1,000
5
7
13
"17
40
175
Average
total
annual i zed
cost, $1,000
8
11
20
25
51
99
Based on a 20-year life and 10 percent interest.
11-17
-------
modified to feed smaller amounts of chlorine, saving 1.5 mg of chlorine per
32
liter. The capital and operating costs for using chlorine dioxide are
presented in Table 11-5. The total annualized costs range from $22,000 for
the smallest plant to $997,000 for the largest plant.
Use of Improved clarification
The costs for improving clarification are based on increasing the alum
dosage by 10 mg/1; installing a polymer feed system which will add polymer at
32
the rate of 0.5 mg/1; and improving the inlet baffling. The total annualized
costs, presented in Table 11-6, range from $17,000 for the smallest system to
$1.12 million for the largest system.
Modifying Chiorination
The costs for modifying chlorination are based on the assumptions that
chlorine will be added to a point following sedimentation and that an alternate
oxidant will replace chlorine (used in prechlorination). The possible alternate
oxidants are potassium permanganate (at a dosage of 0.5 mg/1), hydrogen
peroxide (at 2.0 mg/1), chlorine dioxide (at 0.5 mg/1), and chloramines (at 2.0 mg/1
The average annualized costs presented in Table 11-7 are based on replacing
chlorine with potassium permanganate (the least cost by replacement chemical).
The annualized costs are $7,000 for the smallest size category and $317,000 for
the largest category.
Use of Powdered Activated Carbon
The costs for using PAC are based on the following criteria: all PAC
storage and feed equipment exists on site; the average annual PAC dosage is
7.5 mg/1; the use of PAC results in additional sludge disposal costs; and PAC
34
is delivered in bulk quantities. The annual cost-of using PAC is proportional
to the quantity used and is presented in Table 11-8. The annual cost for the
smallest size category is $32,000, and for the largest size category $3.09 million.
CHLOROFORM CONTROL COST-EFFECTIVENESS
The cost-effectiveness of reducing potential chloroform air emissions
from chlorinated municipal drinking water is the ratio of the cost of
applying a control method in a treatment plant to the resulting reduction in
chloroform emissions. For this analysis, all reductions in chloroform
11-18
-------
TABLE 11-5.
TOTAL ANNUALIZED COST OF CONTROLLING CHLOROFORM BY USING
CHLORINE DIOXIDE35
Plant
capacity,
10s I/day
16
35
69
102
286
1,362
Average
water
production,
106 I/day
10
22
43
64
190
972
Average
capital
cost,
$1,000
47
55
63
120
174
420
Annual ized
capital
cost,
$i,oooa
6
6
7
14
20
49
Average
annual
operating
cost, $1,000
16
29
54
73
201
948
Average
total
annual ized
cost, $1,000
22
35
61
87
221
997
aBased on a 20-year life and 10 percent interest (capital recovery factor = 0.1175).
TABLE 11-6. TOTAL ANNUALIZED COST OF CONTROLLING CHLOROFORM BY
IMPROVING CLARIFICATION
36
Plant
capacity,
106 I/day
16
35
69
102
286
1,362
Average
water
production,
106 I/day
10
22
43
64
190
972
Average
capital
cost,
$1,000
34
46
70
92
198
626
Annual ized
capital
cost,
$1 ,000a
4
5
8
11
23
74
Average
annual
operating
cost, $1,000
13
25
49
71
208
1,046
Average
total
annual ized
cost, $1,000
17
30
57
82
231
1,120
aBased on a 20-year life and 10 percent interest.
11-19
-------
TABLE 11-7. TOTAL ANNUALIZED COST OF CONTROLLING CHLOROFORM BY
MODIFYING CHLORINATION37
Plant
capacity,
106 I/day
16
35
69
102
286
1,362
Based on a
TABLE
Plant
capacity,
106 I/day
16
35
69
102
286
1,362
Average
water
production
10s I/day
10
22
43
64
190
972
20-year life and
Average
capital
cost,
$1,000
15
16
20
25
29
52
10 percent interest.
Annual i zed
capital
cost,
$l,000a
2
2
2
3
3
6
Average
annual
operating
cost, $1,000
5
10
17
23
62
311
11-8. TOTAL ANNUALIZED COST OF CONTROLLING CHLOROFORM
POWDERED ACTIVATED CARBON34
Average
water
production
106 I/day
10
22
43
64
190
972
Average
capital
cost,
$1,000
0
0
0
0
0
0
Annual ized
capital
cost,
$1,000
0
0
0
0
0
0
Average
annual
operating
cost, $1,000
32
70
137
203
606
3,093
Average
total
annual
cost, $1,000
7
12
19
26
65
317
BY USING
Average
total
annual
cost, $1,000
32
70
137
203
606
3,093
11-20
-------
formation in treated water were considered reductions in air emissions. The
cost-effectiveness of the Group I control methods described above are
presented below. The reductions achievable by these control techniques vary
from plant to plant, and depend on the quality of water and treatment
processes in place. The rate of chloroform formation, the chloroform
formation potential, and the effectiveness of any chloroform reduction
technique are dependent upon type and quantity of precursors present as well
as parameters such as pH and temperature. Thus, there is no general one-to-one
correspondence between control technique and level of control achieved.
Because the results of any given control method have been shown to vary
considerably between treatment plants, no typical control efficiency can be
ascribed to a particular control method. Hence, the cost-effectiveness of a
control method cannot be estimated based on an assumed control efficiency.
Cost-effectiveness can, however, be estimated based on the amount of chloroform
"controlled". This amount, in turn, can be calculated from the reduction in
chloroform concentration in treated water resulting from applying a control
method. As shown in Table 11-3, for example, the quantity of chloroform
produced annually in the smallest model plant increases or decreases by
36.5 kg for each 10 yg/1 increase or decrease in chloroform concentration,
regardless of the initial concentration. Because the cost of a control
method for a specific plant size is constant, the cost-effectiveness of
control depends on the quantity of chloroform controlled (or, in other words,
on the decrease in chloroform concentration in treated water resulting from
control). The cost-effectiveness of each control method is presented in
Tables 11-9 through 11-13 for concentration reductions ranging from 10 yg/1
to 100 yg/1. Using these tables, the cost-effectiveness of a particular
control method can be estimated for a plant for varying amounts of control.
The cost-effectiveness is the same for a given increment of concentration
reduction in a plant, whatever the initial concentration. For example,
in the smallest model plant (10 million 1/d average production) the cost-effectivenes
of using chloramines (Table 11-9) will be $110,000/Mg for a 20 yg/1 decrease
in the chloroform concentration whether the concentration was reduced from
120 yg/1 to 100 yg/1 or from 25 yg/1 to 5 yg/1.
11-21
-------
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11-24
-------
CONCLUSIONS
While the amount of chloroform present in drinking water generally is
small, it will evaporate from water during consumer use, exposing consumers
to chloroform air emissions. The trihalomethane drinking water standard
requires the TTHM concentration to be less than 0.10 mg/1, a standard that
most community water supplies have complied with. The Office of State Programs
receives from the States only reports of violations of the MCL by water
treatment systems and therefore has no information on how many systems have
38
had to implement control measures. The cost-effectiveness of the Group I
control techniques presently used is variable, but based on reasonable assump-
tions is shown to range from $2,800/Mg to $877,000/Mg (Tables 11-9 through
11-13). Any reduction in chloroform concentration beyond the present levels
in treatment plants may require control techniques not considered generally
available by the Office of Drinking Water. These treatment techniques certainly
would cost more than the Group I techniques discussed above, and may not be
applicable to every plant.
11-25
-------
REFERENCES
1. Linsley, R.K. and J.B. Franzini. Water-Resources Engineering. Third
Edition. McGraw-Hill Book Company. New York. 1979. p. 429.
2. U.S. Environmental Protection Agency. Treatment Techniques for Controlling
Trihalomethanes in Drinking Water. EPA-600/2-81-156. Municipal
Environmental Research Laboratory. Cincinnati, OH. September 1981. p. 10.
3. Reference 2, pp. 11-21.
4. Reference 1, p. 450.
5. Reference 2, p. 98.
6. Symons, James M., Thomas A. Bellar, J. Keith Carswell, et al. National
Organics Reconnaissance Survey for Halogenated Organics. Journal of
the American Water Works Association, November 1975. pp. 634-651.
7. U.S. Environmental Protection Agency. National Organic Monitoring
Survey. Technical Support Division, Office of Water Supply. Washington,
DC. (no date).
8. Dilling, W.L., N.B. Tefertiller, G.J. Kallos, Evaporation Rates of
Methylene Chloride, Chloroform, 1,1,1-Trichloroethane, Trichloroethylene,
Tetrachloroethylene, and Other Chlorinated Compounds in Dilute Aqueous
Solutions. Environmental Science and Technology. 9_: 833-838, 1975.
9. Reference 2, pp. 43-53.
10. U.S. Environmental Protection Agency. Technologies and Costs for the
Removal of Trihalomethanes From Drinking Water.- Office of Drinking Water.
Washington, DC. February, 1982. p. B-5.
11. Reference 2, p. 90.
12. Reference 10, p. C-15.
13. Federal Register. 48, No. 40, pp. 8406-8414.
14. U.S. Environmental Protection Agency. Ozone, Chlorine Dioxide, and
Chloramines as Alternatives to Chlorine for Disinfection of Drinking
Water - State of the Art. Municipal Environmental Research Laboratory.
Cincinnati, OH. November 1977.
11-26
-------
15. Reference 2, pp. 168-175.
16. Telephone conversation between S. Duletsky, GCA Corporation and K. Carroll,
Hialeah Water Treatment Plant, Miami, FL. January 18, 1983.
17. Reference 2, p. 165.
18. Reference 10, p. 3.
19. Reference 10. p. 4.
20. Reference 2, p. 88.
21. Committee Report. Organic Removal By Coagulation: A Review and Research
Needs. Journal of American Water Works Association. October 1979.
pp. 588-603.
22. Reference 2, p. 100.
23. Reference 2. p. 92.
24. Reference 10, p. 8.
25. Zogorski, J.S., G.D. Allgeiver, and R.L. Malins. Removal of Chloroform
from Drinking Water. University of Kentucky Water Resources Research
Institute, Lexington, KY. Research Report No. 111. June 1978.
26. Reference 10, p. 10.
27. U.S. Environmental Protection Agency. An Assessment of Ozone and Chlorine
Dioxide Technologies for Treatment of Municipal Water Supplies.
Municipal Environmental Research Laboratory. Cincinnati, OH.
EPA-600/2-78-147. August 1978.
28. Design and Operation of Drinking Water Facilities Using Ozone or
Chlorine Dioxide. Proceedings: NEWWA (June 4-5, 1979).
29. Reference 10, p. 14.
30. Reference 10, p. C-3.
31. Reference 10, p. C-16.
32. Reference 10, p. C-4.
33. Reference 10, p. C-5.
34. Reference 10, p. C-20.
35. Reference 10, p. C-17.
36. Reference 10, p. C-18.
11-27
-------
37. Reference 10, p. C-19.
38. Telephone conversation between S. Duletsky, GCA Corporation, and
Nancy Wentworth, U.S. Environmental Protection Agency, Washington, DC,
March 22, 1983.
11-28
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12. MUNICIPAL WASTEWATER TREATMENT
Chloroform is formed in municipal wastewater by the reaction of organic
compounds in wastewater with chlorine containing compounds entering the
sewerage system (such as sodium hypochlorite or bleach), or by the reaction
of organic compounds in the effluent with chlorine used for disinfection.
Tests by EPA's Effluent Guidelines Division on 50 POTW's showed that on
average chloroform concentrations in wastewater dropped 4.6 ug/1, from 15 yg/1
in the influent to 10.4 yg/1 in the secondary effluent. Tests by EPA's
Effluent Guidelines Division on secondary effluent indicate that the average
chloroform concentration in municipal wastewater increases 8 yg/1 following
chlorine disinfection.
In 1982, 8,480 Publicly Owned Treatment Works (POTW's) chlorinated
effluent for disinfection, with a combined flow of 92,081,000 cubic meters
o
per day (24,325 mgd). Applying the 4.6 yg/1 factor to the amount of wastewater
treated, 154.6 Mg/yr of chloroform are emitted from POTW's. Applying the
8 yg/1 factor to the amount of wastewater disinfected annually, 268.9 Mg of
chloroform is generated per year'following wastewater treatment.
Although all of the chloroform is originally in water, tests indicate
that the majority of chloroform generated ends up in the air. Volatilization
from water depends on the solubility, vapor pressure and molecular weight of
the pollutant and physical properties (e.g. flow V-el'ocity, depth, and turbulence)
of the water body and atmosphere above it. Chloroform has a vapor pressure
(Pun) of 0.32 atm at 20°C and a water solubility (S) of 67 mol/m3. Thus,
" -3 3
Henry's law constant (P..-/S) is calculated to be 4.8 x 10 atm-m /mol. When
" -3 3
Henry's law constant is >10 atm-m /mol, volatilization is rapid and the
resistance of the water film dominates volatilization.
CONTROL TECHNIQUES, COSTS, AND COST-EFFECTIVENESS
Control techniques discussed below apply to controlling chloroform
formation during disinfection. Control techniques for limiting chloroform
formation include precursor removal prior to chlorination, and use of a
12-1
-------
disinfectant that does not react with precursors to form chloroform. A third
option, chloroform removal following chlorination, would not be viable because
this method removes chloroform from water by aeration thus hastening the
intermedia transfer to air.
Precursor Removal
Although precursor removal prior to chlorination is possible, the practice
of improved clarification to remove precursors is not practiced by POTW's.
Improved clarification would require addition of coagulants such as iron
salts and aluminum sulfate (alum) during the clarification stage. Addition
of coagulants would increase flocculation and settling of total suspended
solids. This would reduce the amount of precursors because some organic
material is adsorbed on suspended particles.
Best demonstrated efficiency by use of improved clarification at water
treatment plants indicates that improved clarification offers 37 percent
removal efficiency. Thus, on average, chloroform formation in treated
wastewater could be reduced from 8 to 5 yg/1.
Control costs for improving clarification are based on using alum at a
dosage of 10 mg/1; installing a polymer feed system which adds polymer at a
rate of 0.5 mg/1; and improving inlet baffling. These costs were derived
for drinking water treatment systems and applied to POTW's. The total annualized
costs, presented in Table 12-1, range from $17,000 for the smallest system to
$1.12 million for the largest system.
The cost-effectiveness of installing improved clarification would range
from $1.56 million per Mg for the smallest facility to $1.05 million per Mg
for the largest facility (Figure 12-1). Reductions in chloroform formation
potential, costs, and cost-effectiveness are shown" in Table 12-2.
Chlorine Substitution
Chloramines--
Use of chloramines as a drinking water disinfectant has been used in the
United States for many years and could also be used as a substitute for chlorine
at wastewater treatment facilities. Chloramines, unlike chlorine, do not react
with precursor material to form chloroform. Chloramines are produced in treatment
plant water from the reaction of free chlorine and ammonia. When chlorine is
added to water, two reactions take place to form free chlorine species. The
hydrolysis reaction is
12-2
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TABLE 12-1. TOTAL ANNUALIZED COST OF CONTROLLING CHLOROFORM BY
IMPROVING CLARIFICATION
Plant
capacity,
106 I/day
16
35
69
102
286
1,362
Average
water
production,
106 I/day
10
22
43
64
190
972
Average
capital
cost,
$1,000
34
46
70
92
198
626
Annual ized
capital
cost, .
$1 ,000a
4
5
8
11
23
74
Average
annual
operating
cost, $1,000
13
25
49
71
208
1,046
Average
total
annual ized
cost, $1,000
17
30
57
82
231
1,120
Based on a 20-year life and 10 percent interest.
TABLE 12-2. CHLOROFORM REDUCTION POTENTIAL, COSTS, AND COST-EFFECTIVENESS
OF IMPROVED CLARIFICATION
Average amount
of water
treated,
106 I/day
10
22
43
64
190
972
Average CHC13
produced prior
to improved
clarification,
Mg/yra
2.9 x 10'2
6.42 x 10~2
1.25 x 10"1
1.87 x 10"1
5.55 x 10"1 •
2.84 x 10°
Average CHCls
produced after
improved
clarification,
Mg/yrb
1.83 x 10"2
4.02 x 10"2
7.85 x 10"2
1.17 x 10"1
3.47 x 10"1
1.77 x 10°
CHCl^
reduction
potential ,
Mg/yr
1.09 x 10"2
2.4 x 10"--
4.65 x 10"2
7.0 x 1C"2
2.08 x 10"1
1.07 x 10°
Total
annual ized
costs,
$1 ,000
17
30
57
82
231
1,120
Cost-
effectiveness
$106/Mg
1.56
1.25
1.23
1.17
1.11
1.05
a8ased on an average CHC1-, increase of 8 ug/1
h
Based on an average CHClj increase of 5 yg/1
12-3
-------
C12 + H20 = HOC1 + Cl
The ionization reaction is
When ammonia is added to the water the following reaction takes place to form
monochloramine:
HOC! + NH3^=^NH2C1 + H20.
In chlorine-ammonia treatment for primary disinfection, chlorine and ammonia
are added to the water simultaneously or in succession typically at a 4:1
chlorine to ammonia ratio. Although the reaction to form chloramines occurs
in'hundredths of a second at high temperatures and optimum pH (8.3), it proceeds
5
at much slower rates at lower temperatures and other pH values. If ammonia
addition is delayed, or if the reaction between free chlorine and ammonia
proceeds slowly, free chlorine could be present for several minutes or even
several hours.
The ionization reaction described above is highly influenced by pH, with
hypochlorous acid (HOC!) the dominant species at low pH.and hypochlorite ion
(OC1") dominant at high pH values. The chloramine species present are also
influenced by pH. The reaction equation
H+ + 2NH2C1 =^^NH4 + NHCL2
indicates that although mostly monochloramine is formed when excess ammonia is
present at high pH (>8), lowering the pH will cause formation of dichloramine
with the position of this equilibrium determined by the pH. Thus, the pH
determines the relative quantities of species present.
It has been estimated that use of chloramines can reduce chloroform
formation by 90 percent. Thus, on average, chloroform formation in treated
wastewater would be reduced from 8 to 0.8 yg/1 .
For the purpose of estimating costs, the design criteria for using chloramines
are: addition of ammonia to chlorinated water at a 4:1 chlorine to ammonia
ratio to produce chloramines-, an average combined chlorine residual of 3 yg/1;
use of existing chlorine feed equipment and addition of ammonia feed and
storage equipment; and use of either aqueous or anhydrous ammonia. The total
annualized costs for this method, presented in Table 12-3, range from $8,000
for the smallest system to $99,000 for the largest system.
12-4
-------
TABLE 12-3. TOTAL ANNUALIZED COST OF CONTROLLING CHLOROFORM BY USING
CHLORAMINES
Plant
capacity,
106 I/day
16
35
69
102
286
1,362
Average
water
production,
106 I/day
10
22
43
64
190
972
Average
capital
cost,
$1 ,000
28
36
60
70
99
208
Annualized
capital
cost,
$l,000a
3
4
7
8
12
25
Average
annual
operating
cost, $1,000
5
7
13
17
40
175
Average
total
annual i zed
cost, $1,000
8
11
20
25
51
99
Based on a 20-year life and 10 percent interest.
TABLE 12-4 CHLOROFORM REDUCTION POTENTIAL, COSTS, AND COST-EFFECTIVENESS
BY USING CHLORAMINES
Average amount
of water
treated ,
106 I/day
10
22
43
64
190
972
Average CHCl,
produced prior
to use of
choramines,
Mg/yra
2.92 x 10"2
6.42 x 10"2
1.25 x 10"1
1.87 x 10"1
5.55 x 10"1
2.84 x 10°
Average CHC1,
produced after
use of
chloramines,
Mg/yrb
2.92 x 10"3
6.42 x 10"3
1.25 x 10"2
1.87 x 10"2
5.55 x 10"2
2.84 x 10°
CHCU
reduction
potential ,
Mg/yr
2.63 x 10"^ -
5.78 x 10"2
1.13 x 10"1
1.68 x 10"1
5.0 x 10"1
2.56 x 10°
Total
annuali zed
costs,
$1 ,000
8
n
20
25
51
99
Cost-
effectiveness
$1 ,000/Mg
304
190
177
149
102
38.7
aBased on an average CHClj increase of 8 ug/1
Based on an average CHCU increase of 0.8 yg/1
12-5
-------
The cost-effectiveness for using chloramines range from $304,000 per Mg
for the smallest facility to $38,700 per Mg for the largest facility (Figure 12-1)
Reductions in chloroform formation potential, costs, and cost-effectiveness
are shown in Table 12-4.
Chlorine Dioxide--
Laboratory studies and use in drinking water treatment plants show that
chlorine dioxide will disinfect without forming chloroform. Chlorine dioxide
•
equipment can be retrofitted into water treatment plants. Existing chlorination
equipment can be used as a standby. Because chlorine dioxide is unstable, it
must be generated and used on-site. Reactor vessels are available from U.S.
manufacturers, but the simplicity of design has encouraged several plants to
g
fabricate their own. In water treatment plants, chlorine dioxide is usually
generated in reactors by three different methods: reacting chlorine gas and
sodium chlorite; reacting sodium chlorite and a strong acid; or by mixing
sodium hypochlorite, acid, and sodium chlorite. Small amounts of chlorine are
carried over in chlorine dioxide production and form free chlorine in the
water. However, a study has shown that even when the free chlorine concentration
g
is half that of chlorine dioxide, chloroform formation is reduced by 90 percent.
The design criteria for estimating the costs of using chlorine dioxide
are: chlorine dioxide at a dose of 1 mg/1 would replace chlorine as the
disinfectant; a reaction vessel would be used to combine one part chlorine
with one part sodium chlorite; and existing chlorination equipment would be
modified to feed smaller amounts of chlorine, saving 1.5 mg of chlorine per
4
liter. The capital and operating costs for using chlorine dioxide are presented
in Table 12-5. The total annualized costs range from $22,000 for the smallest
plant to $997,000 for the largest plant.
The cost-effectiveness of using chlorine dioxide ranges from $608,000/Mg
for the smallest facility to $370,000/Mg for the largest facility (Figure 12-1).
Reductions in chloroform formation potential, costs, and cost effectiveness
are shown in Table 12-6.
12-6
-------
1
!
1
I
!
,'
i
i ILI -f
i .• 1
1
j
i
i
1
t
i
i
1
f
j
/ / "/
d 1 J
—
1
1
j
j—
1
t" il" 1
Jf / i
3—.—— "-' -fi--"''* +•-" r
-f
OJ
O
T3 O!
Ol -M
-
O.-M
e <^
c en
•r- C
(/I T-
3 i.
3
H- -O
O
O)
CO X!
l/l -r—
OJ X
C O
QJ •<-
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-M OJ
O C
Ol -r-
4- 5-
4- O
CU r—
on
O S-
0 O
I
C\J
r- >:D
-------
TABLE 12-5. TOTAL ANNUALIZED COST OF CONTROLLING CHLOROFORM BY USING
CHLORINE DIOXIDE
Plant
capacity,
10s I/day
16
35
69
102
286
1,362
Average
water
production,
10s I/day
10
22
43
64
190
972
Average
capital
cost,
$1,000
47
55
63
120
174
420
Annual i zed
capital
cost,
$1,000*
6
6
7
14
20
49
Average
annual
operating
cost, $1,000
16
29
54
73
201
948
Average
total
annual i zed
cost, $1,000
22
35
61
87
221
997
Based on a 20-year life and 10 percent interest
TABLE 12-6. CHLOROFORM REDUCTION POTENTIAL, COSTS, AND COST-EFFECTIVENESS
BY USING CHLORINE DIOXIDE
Average amount
of water
treated ,
10s I/day
10
22
43
64
190
972
Average CHClj
produced prior
to use of
chlorine dioxide
Mg/yra
2.92 x 10"2
6.42 x 10"2
1.25 x 10"1
1.87 x 10"1
5.55 x 10""1
2.84 x 10°
Average CHC1,
produced after
use of
chlorine dioxide,
Mg/yrb
2.92 x 10"3
6.42 x TO"3
1.25 x 10"2
1.87 x 10~2
5.55 x 10~2
2.84 x 10"1
CHCU
reduction
potential ,
, Mg/yr
2.63 x 10~2
5.78 x 10~2
1.13 x 10"1
1.68 x 10"1
5.0 x 10'1
2.56 x 10°
Total
annual ized
costs ,
$1 ,000
16
29
54
73
201
948
Cost-
effectiveness
$1 ,000
608
502
479
435
402
370
3Based on an average CHC13 increase of 8 ug/1
3Based on an average CHC1, increase of 0.8 ug/1
12-8
-------
REFERENCES
1. U.S. Environmental Portection Agency. Fate of Priority Pollutants in
Publicly Owned Treatment Works. EPA-440/1-82-303. Effluent Guidelines
Division. Washington, DC. September 1982. p. 69.
2. U.S. Environmental Protection Agency. The 1982 Needs Survey: Conveyance,
Treatment and Control of Municipal Wastewater, Combined Sewer Overflows,
and Stormwater Runoff. EPA-430/19-83-002. Office of Water Program
Operations. Washington, DC. June 1983. p. 92.
3. U.S. Environmental Protection Agency. Treatment Techniques for Controlling
Trihalomethanes in Drinking Water. EPA-600/2-81-156. Municipal Environ-
mental Research Laboratory. Cincinnati, OH. September 1981. p. 100.
4. U.S. Environmental Protection Agency. Technologies and Costs for the
Removal of Trihalomethanes From Drinking Water. Office of Drinking
Water. Washington, DC. February, 1982. p. C-4.
5. Reference 3. pp. 168-175.
6. Reference 3. p. 164.
7. Reference 4. p. C-3.
8. Reference 4. p. 3.
9. Reference 4. p. 4.
12-9
-------
-------
13. GRAIN FUMIGATION
INTRODUCTION
Chloroform is registered as a pesticide to control certain insects which
commonly appear in stored, raw bulk grains. Vulcan Materials Company markets
Chlorofume® FC 30 Grain Fumigant (Reg. No. 5382-15), which contains 72.2 percent
chloroform, 20.4 percent carbon disulfide, and 7.4 percent ethylene dibromide.
Chlorofume is produced as a ready-to-use fumigant. The end users primarily
are small farm establishments which require inexpensive pesticide control.
Chlorofume provides this feature because it can be applied by one person.
Some fumigants require physically turning the supply of stored grain, a labor
intensive and thus costly operation.
Chloroform as an ingredient in pesticides has been subject to considerable
regulatory scrutiny in the last decade. Vulcan Materials Company originally
obtained registration acceptance in 1968. In April 1976, the EPA issued a
"Notice of Presumption Against Continued Registration of a Pesticide Product --
Chloroform (Trichloromethane)." The Notice was issued because of oncogenic
effects in rats and mice as reported in a 1976 study by the National Cancer
Institute. Continued study of chloroform ultimately resulted in returning it
2
to the normal registration process.
Recently there has been considerable debate on the use of ethylene
dibromide (EDB) as a grain fumigant. On February-6^ 1984 EPA cancelled
registrations of pesticide products containing EDB (49 FR 4452). It is not
known whether Vulcan plans to reformulate its product without EDB or not.
EMISSIONS
It is estimated that from 10,000 to 12,000 gallons per year of chloroform
were used in grain fumigants from 1976 to 1979. Vulcan reported sales of
Chlorofume® (72.2 percent chloroform) of 7,000 gallons in 1981. This represents
5,054 gallons or 19,131 liters of chloroform. With a density of 1.48 kg/1,
13-1
-------
28,400 kg or 28.4 Mg of chloroform were used in the application of grain
fumigants. It is assumed that 100 percent of this volatilized during, and
subsequent to, application. Thus 28.4 Mg of chloroform are emitted to air as
a result of grain fumigation.
CONTROL TECHNIQUES
The only viable alternative for controlling releases of chloroform from
grain fumigation would be to substitute another carrier such as carbon
tetrachloride for chloroform. Carbon tetrachloride is used currently as a
carrier in grain fumigation and is used in essentially all other fumigant
mixtures. The best available estimates for average annual carbon tetra-
chloride use are 11,500 to 14,800 Mg between 1976 and 1979,3 and 12,800 Mg
4
for 1977 and 1978. Thus, chloroform accounts for only 0.2 percent of the
carriers used in grain fumigation, with carbon tetrachloride accounting for
the remainder.
13-2
-------
REFERENCES
1. Rehm, R.M., et. al. Chloroform Materials Balance (Draft Report). Prepared
by GCA/Technology Division for U.S. Environmental Protection Agency, Office
of Toxics Integration,. Washington, DC. EPA Contract No. 68-02-3168, Work
Assignment No. 69. December 1982. p. 77.
2. U.S. Environmental Protection Agency. Chloroform Position Document 2.
Office of Pesticides and Toxic Substances. Washington, DC. September 1982.
pp. 1-3.
3. Holtorf, R.C., and G.F. Ludvik. Grain Fumigants: An Overview of Their
Significance of U.S. Agriculture and Commerce and Their Pesticide Regulatory
Implications. U.S. Environmental Protection Agency, Washington, DC,
September 1981, p. 3.
4. Development Planning and Research Associates, Inc. Preliminary Benefit
Analysis: Cancellation of Carbon Tetrachloride in Fumigants for Stored
Grain. U.S. Environmental Protection Agency, Washington, DC, April 1980.
p. V-3.
13-3
-------
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/3-85-026
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
October 1985
Survey of Chloroform Emission Sources
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Sam Dulestsky (EPA), Richard Rehm (GCA Corporation),
Mark Smith (GCA Corporation)
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Office of Air Quality Planning and Standards
Environmental Protection Agency
Research Triangle Park, North Carolina
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-02-3510
Work Assignment 39
12. SPONSORING AGENCY NAME AND ADDRESS
DAA for Air Quality Planning and Standards
Office of Air and Radiation
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final __
14. SPONSORING AGENCY CODE
EPA/200/04
15. SUPPLEMENTARY NOTES
Public
16. ABSTRACT
The potential public health impact of chloroform exposure is being investigated.
This document contains information onthe sources of chloroform emissions, current
emission levels, control methods that could be used to reduce chloroform emissions;
and cost estimates for employing controls.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATl Field/Group
Air pollution
Pollution Control
Synthetic organic chemical manufacturing
industry
Chloroform
Air pollution control
13B
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (This Report/
Unclassified
21. NO. OF PAGES
221
Unlimited
20. SECURITY CLASS (Thispage/
Unclassified
22. PRICE
EPA Form 2220-1 (R«v. 4-77) PREVIOUS EDITION is OBSOLETE
------- |