United States
Environmental Protection
Agency
Office of Air Quality
Pluming and Standards
Research Triangle Park. NC 27711
EPA-454/R-93-045
February 1994
LOCATING AND ESTIMATING
Am EMISSIONS
FROM SOURCES OF
METHYL CHLOROFORM
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EPA-454/R-93-045
LOCATING AND ESTIMATING AIR EMISSIONS
FROM SOURCES OF METHYL CHLOROFORM
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
February 1994
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DISCLAIMER
This report has been reviewed by the Office of Air Quality Planning and Standards, and
has been approved for publication. Any mention of tradenames or commercial products is not
intented to constitute endorsement or recommendation for use.
11
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CONTENTS
Section Page
DISCLAIMER ii
LIST OF FIGURES v
LIST OF TABLES vi
1.0 PURPOSE OF DOCUMENT 1-1
1.1 Reference for Section 1.0 1-5
2.0 OVERVIEW OF DOCUMENT CONTENTS 2-1
2.1 References for Section 2.0 2-5
3.0 BACKGROUND 3-1
3.1 Nature of Pollutant 3-1
3.2 Regulatory Actions Affecting Methyl Chloroform Production and Use .... 3-4
3.3 Overview of Production and Use 3-7
3.4 References for Section 3.0 3-10
4.0 EMISSIONS FROM METHYL CHLOROFORM PRODUCTION 4-1
4.1 Production Process Descriptions 4-2
4.1.1 Hydrochlorination of Vinyl Chloride 4-4
4.1.2 Hydrochlorination of Vinylidene Chloride 4-7
4.1.3 Noncatalytic Chlorination of Ethane 4-7
4.2 Emissions 4-10
4.2.1 Process Emissions 4-12
4.2.2 Storage Emissions 4-13
4.2.3 Equipment Leak Emissions (Fugitive Emissions) 4-15
4.3 References for Section 4.0 4-19
5.0 EMISSIONS FROM MAJOR USES OF METHYL CHLOROFORM 5-1
5.1 Solvent Cleaning 5-2
5.1.1 Process Description 5-3
5.1.2 Emissions 5-5
5.2 Paint and Ink Manufacturing 5-8
5.2.1 Process Description 5-11
5.2.2 Emissions 5-15
5.3 Aerosol Manufacturing 5-16
5.4 Adhesive Manufacturing 5-18
5.5 Chemical Intermediates 5-20
5.6 Miscellaneous End Uses of Methyl Chloroform 5-22
5.7 References for Section 5.0 5-24
in
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TABLE OF CONTENTS (continued)
Section Page
6.0 RESIDUAL AND BY-PRODUCT EMISSIONS OF
METHYL CHLOROFORM 6-1
6.1 Surface Coating Operations 6-1
6.1.1 Process Description 6-3
6.1.2 Emissions 6-3
6.2 Wastewater Treatment Processes 6-7
6.3 Pulp and Paper Production 6-10
6.3.1 Description of Pulp Processing 6-10
6.3.2 Atmospheric Emissions from Pulp Processing 6-12
6.4 References for Section 6.0 6-13
7.0 AMBIENT AIR AND STATIONARY SOURCE TEST PROCEDURES 7-1
7.1 EPA Method TO-1 7-1
7.2 EPA Method TO-2 7-2
7.3 EPA Method TO-14 7-5
7.4 EPA Method 0030 7-8
7.5 EPA Method 5040 7-8
7.6 References for Section 7.0 7-12
APPENDIX A POTENTIAL SOURCE CATEGORIES OF METHYL
CHLOROFORM EMISSIONS A-l
APPENDIX B LISTS OF PAINT, INK, AND PRINTING FACILITIES WITH
ANNUAL SALES GREATER THAN $1 MILLION B-l
APPENDIX C SUMMARY OF EMISSION FACTORS LISTED
IN THIS DOCUMENT C-l
IV
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LIST OF FIGURES
Number Page
3-1 Chemical Use Tree for Methyl Chloroform 3-8
4-1 Process Flow Diagram for the Hydrochlorination of Vinyl Chloride 4-5
5-1 Flow Diagram of the Paint and Ink Manufacturing Process 5-14
6-1 Flow Diagram of a Surface Coating Operation 6-4
6-2 Typical Kraft Sulfate Pulping and Recovery Process 6-11
7-1 EPA Method TO-1 Sampling System 7-3
7-2 Tenax® Cartridge Design 7-4
7-3 Carbon Molecular Sieve Trap (CMS) Construction 7-6
7-4 Canister Sampling System 7-7
7-5 Schematic of Volatile Organic Sampling Train (VOST) 7-9
7-6 Schematic Diagram of Trap Desorption/Analysis System 7-11
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LIST OF TABLES
Number Page
3-1 Chemical Identification of Methyl Chloroform 3-2
3-2 Physical and Chemical Properties of Methyl Chloroform 3-3
3-3 Corporate Reduction and Phase-out Policies for Methyl Chloroform 3-5
3-4 End Uses of Methyl Chloroform 3-9
4-1 Methyl Chloroform Production Locations and Capacities 4-2
4-2 Estimated Domestic U.S. Supply and Demand of Methyl Chloroform 4-3
4-3 Methyl Chloroform Production Emissions 4-11
4-4 Methyl Chloroform Emission Factors from Methyl Chloroform Production 4-12
4-5 Average Emission Factors for Fugitive Equipment Leak Emissions 4-16
4-6 Control Techniques and Efficiencies Applicable to Equipment Leak
Emissions 4-18
5-1 Summary of Emissions Tests on Idling OTVC (Using Methyl Chloroform
as Solvent) 5-8
5-2 Summary of Emissions Tests on Working OTVC (Using Methyl Chloroform
as Solvent) 5-9
5-3 Estimated Consumption of Solvents in Paints and Coatings, by Market 5-12
5-4 Aerosol Products Containing Methyl Chloroform 5-17
5-5 Adhesive Subcategories and Number of Facilities Using Methyl Chloroform . . . 5-19
6-1 Methyl Chloroform Source Categories in Surface Coating Operations 6-2
VI
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EXECUTIVE SUMMARY
Emissions of methyl chloroform into the atmosphere are of special significance because
of the 1990 Clean Air Act Amendments. These amendments mandate that methyl chloroform
emissions be subject to standards that allow for the maximum degree of reduction of emissions
and that, by 1995, a list of source categories be established that accounts for no less than 90
percent of methyl chloroform emissions. This document is designed to assist groups interested
in inventorying air emissions of methyl chloroform by providing a compilation of available
information on sources and emissions of this substance.
Methyl chloroform, also commonly known as 1,1,1, trichloroethane, is a man-made
chlorinated solvent. In the U.S., methyl chloroform is produced by three facilities. All three
produce methyl chloroform by the hydrochlorination of vinyl chloride to yield 1,1-dichloroethane,
which is then thermally dechlorinated to methyl chloroform. The total annual production capacity
in the U.S. for 1992 was 477,000 megagrams (1050 million pounds).
Metal cleaning accounts for 49% of the total methyl chloroform used. It is also used for
the manufacture of aerosols, adhesives, coating and inks, as chemical intermediates, and in the
textiles and electronics industries.
At the time of publication of this document, estimates of nationwide methyl chloroform
emissions were not available. Updates to this document will attempt to incorporate any
nationwide emission estimates subsequently developed.
It is important to note that production of methyl chloroform will decline as a result of the
Montreal Protocol on Substances that Deplete the Ozone Layer (Montreal Protocol) and Title VI
of the 1990 Clean Air Act Amendments. Methyl chloroform is classified as a controlled
vn
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substance and is scheduled for phase-out by 2005 under the Montreal Protocol and 2002 under
the amendments. The EPA also published a final rule in the Federal Register on December 10,
1993 that accelerates the schedule for phase-out of methyl chloroform production to January 1,
1996.
Vlll
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SECTION 1.0
PURPOSE OF DOCUMENT
The Environmental Protection Agency (EPA) and State and local air pollution control
agencies are becoming increasingly aware of the presence of substances in the ambient air that
may be toxic to humans at certain concentrations. This awareness, in turn, has led to attempts
to identify source/receptor relationships for these substances and to develop control programs to
regulate emissions. Unfortunately, very little information is available on the ambient air
concentrations of these substances or on the sources that may be discharging them to the
atmosphere.
To assist groups interested in inventorying air emissions of various potentially toxic
substances, EPA is preparing a series of documents such as this that compiles available
information on sources and emissions of these substances. Prior documents in the series are
listed below:
Substance EPA Publication Number
Acrylonitrile EPA-450/4-84-007a
Carbon Tetrachloride EPA-450/4-84-007b
Chloroform EPA-450/4-84-007c
Ethylene Dichloride EPA-450/4-84-007d
Formaldehyde (Revised) EPA-450/2-91-012
Nickel EPA-450/4-84-007f
Chromium EPA-450/4-84-007g
Manganese EPA-450/4-84-007h
Phosgene EPA-450/4-84-007i
Epichlorohydrin EPA-450/4-84-007J
Vinylidene Chloride EPA-450/4-84-007k
Ethylene Oxide EPA-450/4-84-0071
Chlorobenzenes EPA-450/4-84-007m
Polychlorinated Biphenyls (PCBs) EPA-450/4-84-007n
Polycyclic Organic Matter (POM) EPA-450/4-84-007p
Benzene EPA-450/4-84-007q
Organic Liquid Storage Tanks EPA-450/4-88-004
Coal and Oil Combustion Sources EPA-450/2-89-001
Municipal Waste Combustors EPA-450/2-89-006
Perchloroethylene and Trichloroethylene EPA-450/2-90-013
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Substance EPA Publication Number
1,3-Butadiene EPA-450/2-89-021
Chromium (supplement) EPA-450/2-89-002
Sewage Sludge EPA-450/2-90-009
Styrene EPA-450/4-91-029
Methylene Chloride EPA-454/R-93-006
This document deals specifically with methyl chloroform. Its intended audience includes
federal, State, and local air pollution personnel and others who are interested in locating potential
emitters of methyl chloroform, and making gross estimates of air emissions therefrom.
Because of the limited amounts of data available on potential sources of methyl
chloroform emissions, and since the process configurations, control equipment, and operating
procedures of many sources will not be the same as those described here, this document is best
used as a primer to inform air pollution personnel about (1) the types of sources that may emit
methyl chloroform, (2) process variations and release points that may be expected within these
sources, and (3) available emissions information indicating the potential for methyl chloroform
to be released into the air from each operation.
The reader is strongly cautioned against using the emissions information contained in this
document to try to develop an exact assessment of emissions from any particular facility.
Because insufficient data are available to develop statistical estimates of the accuracy of these
emission factors, no estimate can be made of the error that could result when these factors are
used to calculate emissions from any given facility. It is possible, in some extreme cases, that
order-of-magnitude differences could result between actual and calculated emissions, depending
on differences in source configurations, control equipment, and operating practices. Thus, in
situations where an accurate assessment of methyl chloroform emissions is necessary, source-
specific information should be obtained to confirm the existence of particular emitting operations,
the types and effectiveness of control measures, and the impact of operating practices. A source
test and in some cases a material balance should be considered as the best means to determine
air emissions directly from an operation.
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In addition to the information presented in this document, another potential source of
emissions data for methyl chloroform is the Toxic Chemical Release Inventory (TRI) database
required by Section 313 of Title III of the Superfund Amendments and Reauthorization Act of
1986 (SARA 313).1 SARA 313 requires owners and operators of certain facilities that
manufacture, import, process, or otherwise use certain toxic chemicals to report annually their
releases of these chemicals to any environmental media. As part of SARA 313, EPA provides
public access to the annual emissions data. The TRI data include general facility information,
chemical information, and emissions data. Air emissions data are reported as total facility release
estimates, broken out into fugitive and point components. No individual process or stack data
are provided to EPA. The TRI requires the use of available stack monitoring or measurement
of emissions to comply with SARA 313. If monitoring data are unavailable, emissions are to be
quantified based on best estimates of releases to the environment.
The reader is cautioned that the TRI will not likely provide facility, emissions, and
chemical release data sufficient for conducting detailed exposure modeling and risk assessment.
In many cases, the TRI data are based on annual estimates of emissions (i.e., on emission factors,
material balances, engineering judgement). Although the TRI database was consulted during the
development of this report, it should be referred to as an additional source to locate potential
emitters of methyl chloroform, and to make preliminary estimates of air emissions from these
facilities. In addition, the reader should be cautioned that only facilities using greater than 25,000
pounds of methyl chloroform in production activities (e.g., incorporated into the product) or
greater than 10,000 pounds for other purposes (e.g., degreasing) would be required to file
emissions under SARA 313. Facilities with smaller uses would not necessarily appear in the TRI
database. To obtain an exact assessment of air emissions from processes at a specific facility,
source tests or in some cases detailed material balance calculations should be conducted, and
detailed plant site information should be compiled.
Each L&E document, as standard procedure, is sent to government, industry, and
environmental groups wherever EPA is aware of expertise. These groups are given the
opportunity to review the document, comment, and provide additional data where applicable.
Where necessary, the documents are then revised to incorporate these comments. Although these
1-3
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documents have undergone extensive review, there may still be shortcomings. Comments
subsequent to publication are welcome and will be addressed based on available time and
resources. In addition, any information is welcome on process descriptions, operating parameters,
control measures, and emissions information that would enable EPA to improve the contents of
this document. Comments and information may be sent to the following address:
Chief, Emission Factor and Methodologies Section
Emission Inventory Branch, (MD-14)
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
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1.1 REFERENCE FOR SECTION 1.0
1. Toxic Chemical Release Reporting: Community Right-To-Know. Federal Register
52(107): 21152-21208. June 4, 1987.
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SECTION 2.0
OVERVIEW OF DOCUMENT CONTENTS
The purpose of this document is to assist federal, State, and local air pollution agencies
and others who are interested in locating potential air emitters of methyl chloroform and making
gross estimates of air emissions therefrom. Because of the limited background data available,
the information summarized in this document does not and should not be assumed to represent
the source configuration or emissions associated with any particular facility.
This section provides an overview of the contents of this document. It briefly outlines
the nature, extent, and format of the material presented in the remaining sections of this report.
Section 3.0 of this document briefly summarizes the physical and chemical characteristics
of methyl chloroform, and provides an overview of its production and use. This background
section may be useful to someone who needs to develop a general perspective on the nature of
this substance and how it is manufactured and consumed.
Section 4.0 of this document focuses on major production source categories that may
discharge air emissions containing methyl chloroform. Section 5.0 discusses the uses of methyl
chloroform as industrial feedstocks and major solvent uses, particularly degreasing and coating
operations. Section 6.0 addresses emissions as a result of releases from methyl chloroform-
containing products after manufacture and emissions resulting from the manufacture of products
other than methyl chloroform, or as a by-product of processes (e.g., kraft pulping). Example
process descriptions and flow diagrams are provided in addition to available emission factor
estimates for each major industrial source category described in Sections 4.0, 5.0, and 6.0.
Individual companies involved with either the production or use of methyl chloroform are
reported throughout the document. The information reported is extracted primarily from trade
publications.
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Section 7.0 of this document summarizes available procedures for source sampling and
analysis of methyl chloroform. The summaries provide an overview of applicable sampling and
analytical procedures, citing references for those interested in conducting source tests.
Appendix A identifies potential source categories of methyl chloroform emissions by
Standard Industrial Classification (SIC) code and associated description. These potential source
categories do not necessarily denote significant sources of methyl chloroform emissions. The
readers interested in cross referencing SICs with Source Classification Codes (SCCs) and
associated descriptions should consult the Crosswalk/Air Toxic Emission Factor Database
Management System, Version 1.2 (October 1991) and/or the Volatile Organic Compound
(VOC)/Particulate Matter (PM) Speciation Database Management System, Version 1.4 (October
1991).1'2 Appendix B lists paint and ink manufacturing facilities and printing facilities with sales
greater than $1,000,000. Appendix C summarizes, in table format, all emission factors listed in
this document.
Each emission factor listed in Sections 3.0 through 6.0 has been assigned an emission
factor grade based on the criteria for assigning data quality and emission factor ratings as
required in the document Technical Procedures for Developing AP-42 Emission Factors and
Preparing AP-42 Sections. These criteria for rating test data used to develop emission factors
are presented below.3 The data used to develop emission factors are rated as follows:
A - Tests performed by a sound methodology and reported in enough detail for
adequate validation. These tests are not necessarily EPA reference test methods,
although such reference methods are certainly to be used as a guide.
B - Tests that are performed by a generally sound methodology but lack enough detail
for adequate validation.
C - Tests that are based on a nonvalidated or draft methodology or that lack a
significant amount of background data.
D - Tests that are based on a generally unacceptable method but may provide an
order-of-magnitude value for the source.
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Because of the almost impossible task of assigning a meaningful confidence limit to
industry-specific variables (i.e.., sample size vs. sample population, industry and facility
variability, method of measurement), the use of a statistical confidence interval for an emission
factor is not practical. Therefore, some subjective quality rating is necessary. The following
emission factor quality ratings are applied to the emission factor tables.
A - Excellent. The emission factor was developed only from A-rated test data taken from
many randomly chosen facilities in the industry population. The source category* is
specific enough to minimize variability within the source category population.
B - Above average. The emission factor was developed only from A-rated test data from
a reasonable number of facilities. Although no specific bias is evident, it is not clear if
the facilities tested represent a random sample of the industries. As in the A rating, the
source category is specific enough to minimize variability within the source category
population.
C - Average. The emission factor was developed only from A- and B-rated test data from
a reasonable number of facilities. Although no specific bias is evident, it is not clear if
the facilities tested represent a random sample of the industry. As in the A rating, the
source category is specific enough to minimize variability within the source category
population.
D - Below average. The emission factor was developed only from A- and B-rated test
data from a small number of facilities, and there may be reason to suspect that these
facilities do not represent a random sample of the industry. There also may be evidence
of variability within the source category population. Limitations on the use of the
emission factor are footnoted in the emission factor table.
E - Poor. The emission factor was developed from C- and D-rated test data, and there
may be reason to suspect that the facilities tested do not represent a random sample of
the industry. There also may be evidence of variability within the source category
population. Limitations on the use of these factors are always footnoted.
U - Unrated or Unratable. The emission factor was developed from suspect data with no
supporting documentation to accurately apply an A through E rating. A "U" rating may
be applied in the following circumstances:4
- a gross mass balance estimation
- QA/QC deficiencies found with C- and D-rated test data
- gross engineering judgement
- technology transfer
* Source category: A category in the emission factor table for which an emission factor has been calculated; generally a single process.
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This document does not contain any discussion of health or other environmental effects
of methyl chloroform. It does include a discussion of ambient air monitoring techniques;
however, these ambient air monitoring methods may require modifications for stack sampling and
may affect data quality.
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2.1 REFERENCES FOR SECTION 2.0
1. U.S. Environmental Protection Agency. Crosswalk/Air Toxic Emission Factor Database
Management System, Version 1.2. Office of Air Quality Planning and Standards.
Research Triangle Park, NC. October 1991.
2. U.S. Environmental Protection Agency. Volatile Organic Compound (VOC)/Particulate
Matter (PM) Speciation Database Management System, Version 1.4. Office of Air
Quality Planning and Standards, Research Triangle Park, NC. September 1990.
3. U.S. Environmental Protection Agency. Technical Procedures for Developing AP-42
Emission Factors and Preparing AP-42 Sections, Draft Document. Office of Air Quality
Planning and Standards. Research Triangle Park, NC. March 1992.
4. Group discussion meeting on applying "U" rating to emission factors. Anne Pope, EIB;
Robin Baker Jones, Midwest Research Institute; Garry Brooks, Radian Corporation; and
Theresa Moody, TRC Environmental Corporation.
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SECTION 3.0
BACKGROUND
3.1 NATURE OF POLLUTANT
Methyl chloroform or 1,1,1-trichloroethane, is a man-made chlorinated solvent. The first
commercial success of methyl chloroform was as a replacement for the toxic carbon tetrachloride
in room temperature metal cleaning operations.1'2 Cleaning operations, including cold cleaning
and vapor degreasing, remain the largest end use of methyl chloroform.
Methyl chloroform's molecular structure is represented as:
Cl H
Cl—C—C—H
Cl H
Table 3-1 summarizes the chemical identification information for methyl chloroform, and
Table 3-2 presents methyl chloroform's chemical and physical properties. Methyl chloroform
tends to decompose in the presence of heat, light, oxygen, and water. Decomposition may be
accelerated by the presence of metals or metal salts and by the decomposition products of
chlorohydrocarbons. For this reason, methyl chloroform is normally stabilized prior to shipment
with one of three types of stabilization chemicals:
antioxidants
• compounds which will neutralize the autocatalytic action of products resulting during
decomposition reactions
• chemicals that inhibit catalytic action of metals
Stabilizers, such as 1,2-butylene oxide, cyclohexene oxide, nitromethane, 1,4-dioxane,
diallylamine, or cyclic amines, are often added to methyl chloroform in quantities up to five
percent to prevent decomposition. Stabilization is especially important if the methyl chloroform
5-1
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TABLE 3-1.
CHEMICAL IDENTIFICATION OF METHYL CHLOROFORM
Chemical name
Methyl chloroform
Synonyms
1,1,1-trichloroethane; ethylidine chloride;
methyltrichloromethane; trielene; algylen;
trichloromethylmethane; chloroethane;
inhibisol; trichloran; gemalgene; TCA;
TCEA; aerothene; oc-Trichloroethane;
1,1,1-TCE; 1,1,1-Tri; trichloroethane
Molecular formula
C2H3C13
Identification numbers:3
CAS Registry
NIOSH RTECS
EPA Hazardous Waste
OHM/TADS
DOT/UN/NA/IMCO
HSDB
STCC
71-55-6
KJ 2975000
U226, F002
8100101
UN 2831; 1,1,1-Trichloroethane
IMO 6.1; 1,1,1-Trichloroethane
157
49 411 76; 1,1,1-Trichloroethane
Source: References 3-5.
aCAS (Chemical Abstracts Services); NIOSH (National Institute of Occupational Safety
and Health); RTECS (Registry of Toxic Effects of Chemical Substances);
EPA (Environmental Protection Agency); OHM/TADS (Oil and Hazardous Materials/
Technical Assistance Data System); DOT/UN/NA/IMCO (Department of Transportation/
United Nations/North America/International Maritime Dangerous Goods Code); HSDB
(Hazardous Substance Database); STCC (Standard Transport Commodity Code).
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TABLE 3-2.
PHYSICAL AND CHEMICAL PROPERTIES OF METHYL
CHLOROFORM
Property
Molecular weight (grams)
Melting point
Boiling point (760 mm Hg)
Density, g/cm
at 25°C (77°F)
at 20°C (68°F)
Physical state (ambient conditions)
Color
Specific heat at 20°C (68°F)
liquid
gas
Heat capacity at 25°C (77°F) and 760 mm Hg
liquid
gas
Solubility:
Water at 20°C (68°F)
Organic solvents
Partition coefficients:
LogjQ octanol/water
Vapor pressure at 20°C (68°F)
at 40°C(104°F)
Autoignition temperature
Critical temperature
Critical pressure
Binary azeotropes, boiling point
with 4.3 percent water
with 23 percent methanol
with 17.4 percent ethanol
with 17 percent isopropyl alcohol
with 17.2 percent tert-butyl alcohol
Conversion factors (Vapor weight to volume)
Viscosity at 20°C (68°F)
Value
133.42
-30.4°C (-22.7°F)
74.1°C (165. 4°F)
1.136
1.324
Liquid
Clear
1.004 J/g
0.782 J/g
34.4 cal/gmol
22.4 cal/gmol
Insoluble (0.095 g in 100 g water)
0.034 g (water in 100 g methyl chloroform)
Soluble in acetone, benzene, carbon tetrachloride,
methanol and ether
2.49 (20°C or 68°F)
13.3 kPa (99.8 mm Hg)
31.7 kPa (237.8 mm Hg)
537°C (999°F)
311. 5°C (592.7°F)
4.48 MPa (44.2 atm)
65.0°C (149°F)
55.5°C (131. 9°F)
64.4°C (147.9°F)
68.2°C (154.8°F)
70.2°C (158. 4°F)
1 ppm = 5.46 mg/L (25°C or 77°F)
0.858 mPa's
Source: References 2,4-8.
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is to be used for vapor degreasing operations where the chemical will be exposed to high
temperatures, metals, and other contaminants.9
Methyl chloroform released to the water is expected to have an evaporative half-life
ranging from several hours to a few weeks depending on wind and mixing conditions.10 Methyl
chloroform is released to the atmosphere during its manufacture and from the use of methyl
chloroform-containing materials. Methyl chloroform has also been detected in small amounts in
the ambient air and wastewater at kraft pulp mills and wastewater treatment facilities.10'11
Methyl chloroform is relatively stable in the atmosphere with an estimated half-life of 6
months to 25 years.12 Only a small portion of the methyl chloroform released to the air is
removed in the troposphere (i.e., the region of the atmosphere extending from the ground to as
high as 15 kilometers) by reaction with hydroxyl radicals. For this reason, the EPA has
identified methyl chloroform as being negligibly photochemically reactive. However, the portion
that does not react in the troposphere may be conveyed to the stratosphere. There, the methyl
chloroform participates in the depletion of the stratospheric ozone layer.13 Methyl chloroform
is the highest volume ozone-depleting chemical and is responsible for 16 percent of the ozone-
destroying chlorine now in the stratosphere from anthropogenic sources.14'15
3.2 REGULATORY ACTIONS AFFECTING METHYL CHLOROFORM PRODUCTION
AND USE
Consumption and production of methyl chloroform will decline as a result of the
implementation of the 1987 Montreal Protocol on Substances that Deplete the Ozone Layer and
Title VI of the 1990 Clean Air Act Amendments (CAAA).16 Under both of these provisions,
methyl chloroform is classified as a controlled substance scheduled for phase-out within the next
ten years (i.e., 2005 under the 1990 Revision of the Montreal Protocol and 2002 under the 1990
CAAA).17'18 In addition to the scheduled regulatory phase-outs, several corporations have
voluntarily implemented reduction and phase-out policies. A summary of these corporate
strategies is included in Table 3-3.
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TABLE 3-3.
CORPORATE REDUCTION AND PHASE-OUT POLICIES FOR
METHYL CHLOROFORM
Year
1990
1991
1992
1995
2000
Type of Policy/
Implementing
Corporation
Significant
reductions:
Eveready
Mobil
Discontinue use:
Fischer Controls
International
Significant
reductions:
Boeing
Discontinue use:
MEMC Electronic
Materials
Significant
reductions:
Boeing
Significant
reductions:
American
Electronics
Association
Location
Asheboro, NC
Shawnee, OK
Marshalltown, IA
Company-wide
Spartanburg, SC
Company-wide
Member companies
Comments
(90% reduction from
1988 level.) Replace
use in maintenance-
rebuild area.
20% reduction
50% reduction
40% overall
emissions reduction
Source: Reference 14.
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Both the Montreal Protocol and the CAAA Title VI contain several definitions and
exemptions which apply to methyl chloroform production and consumption. Title VI defines a
controlled substance as
...(a listed substance) existing alone or in a mixture, but excluding any such
substance or mixture that is in a manufactured product other than a container used
for the transportation or storage of the substance or mixture. ...If a listed
substance or mixture must first be transferred from a bulk container to another
container, vessel, or piece of equipment in order to realize its intended use, the
listed substance or mixture is a controlled substance.
Production, as defined by the CAAA, is the
manufacture of a substance from any raw material or feedstock chemical, but does
not include the manufacture of a substance that is used and entirely consumed
(except for trace quantities) in the manufacture of other chemicals or the reuse or
recycling of a substance.
Coincidental unavoidable by-product (CUBP) is defined by the CAA, as "a product that is
unintentionally manufactured in the course of manufacturing another product." While spills and
vent releases of methyl chloroform in excess of 45 kgs (100 Ibs) per event are "produced" and
"controlled," the production of a CUBP immediately contained and destroyed by the producer
using the maximum achievable control technology (MACT) is considered neither produced nor
controlled.15 Another production exception is the "use and entire consumption in the manufacture
of other chemicals." In order to fit this clause, methyl chloroform must be transformed or broken
down so that it is physically impossible to recover after its use.18 According to clarifications
provided by EPA, commercial processes in which methyl chloroform is used and entirely
consumed but not transformed (e.g., uses of methyl chloroform as reaction inhibitors, solvents,
or inert direct coolants) are controlled and subject to the phase-out requirements.17'18 This means
that most of the end-uses of methyl chloroform (e.g., solvent degreasing, adhesives, and coatings
and inks) will fall under the phase-out requirements.15
-------
Section 604(d)(l) of the CAAA provides for another exemption to the 1992 phase-out
requirements for essential uses of methyl chloroform for which no safe and effective substitute
is available. One essential use is anticipated to be in the limited production of halon-1211,
halon-1301, and halon-2402 for purposes of aviation safety. Another potential essential use is
in the nondestructive testing for metal fatigue and corrosion of existing airplane engines and
airplane parts susceptible to metal fatigue. The third potential exception for essential uses of
methyl chloroform is for use in medical devices.18 Facilities using methyl chloroform in
manufacturing must label the product stating that a stratospheric ozone depleting substance has
been used. However, the EPA will not make a final determination on essential use exemptions
until the availability of methyl chloroform is more constrained.
3.3 OVERVIEW OF PRODUCTION AND USE
The total annual capacity of methyl chloroform manufacturing facilities in the United
States has been 477 million kgs (1,050 million Ibs) for the years 1986 through 1992.3'19 The
three domestic facilities known to manufacture methyl chloroform do so by the hydrochlorination
of vinyl chloride to yield 1,1-dichloroethane, which is then thermally chlorinated to methyl
chloroform. Currently, production of methyl chloroform exceeds demand.15
The primary end use for methyl chloroform is metal cleaning. Together, vapor degreasing
and cold cleaning account for 49 percent of methyl chloroform end use.19 Other end uses include
aerosols (12 percent), adhesives (10 percent), chemical intermediates (10 percent), coatings and
inks (7 percent), textiles (4 percent), electronics (3 percent), and miscellaneous uses (5 percent).19
Facilities in every category of the manufacturing sector (represented by SIC codes 20-39) have
reported emissions of methyl chloroform in the Toxic Chemical Release Inventory.14'20 Figure 3-1
and Table 3-4 present some of the end uses of methyl chloroform. These uses will be discussed
in detail in Sections 5.0 and 6.0. A list of all potential methyl chloroform emission sources
organized according to SIC code and associated description is presented in Appendix A. It is
important to note that these source categories do not necessarily denote significant sources of
methyl chloroform emissions.
5-7
-------
Methyl Chloroform
Production Method
Use
Percent
Hydrochlorination
of Vinyl Chloride
.Vapor Degreasing 31
Cold Cleaning
.Aerosols
.Adhesives
18
12
10
.Chemical Intermediates 10
Coating and Inks
.Textiles
7
4
Electronics
Miscellaneous Uses
Figure 3-1. Chemical use tree for methyl chloroform.3'19
3-8
-------
TABLE 3-4.
END USES OF METHYL CHLOROFORM
Use Category
End Use
Metal Cleaning
cold cleaning
conveyorized non-boiling degreasers
conveyorized vapor degreasers
Aerosols
household products
automotive products
coatings and finishes
personal care products
pesticides
Adhesives
consumer and industrial formulations
substitute for other solvents in urethane adhesives
Chemical Intermediates
hydrochlorofluorocarbon (HCFC) 142b
hydrochlorofluorocarbon (HCFC) 141b
Coatings and Inks
traffic paints (lane lines, road arrows)
grease cutter
cleaner for typewriter keys
gravure and flexographic inks
Textiles
scouring agents
cleaning textile and machinery tools
dye carrier
spotting fluid
Electronics
cleaner to remove flux on printed circuit boards
plasma etchant gases
dry film photoresist developer
Miscellaneous
drain cleaners
septic tank cleaners
pharmaceutical extractant
glossing and weatherproofmg leather products
plastic film cleaners (movie, video, TV film)
coolant in cutting oils
Source: References 9, 11.
5-9
-------
3.4 REFERENCES FOR SECTION 3.0
1. Archer, W.L, "Other Chloroethanes," Kirk-Othmer Encyclopedia of Chemical Technology,
Third Edition. Vol. 5. John Wiley and Sons, New York, NY. pp. 722-742. 1979.
2. Considine, Douglas M., ed., Chemical and Process Technology Encyclopedia. McGraw-
Hill Book Company, New York, NY. 1974.
3. "1,1,1-Trichloroethane," Chemical Products Synopsis. Mannsville Chemical Products,
Ashbury Park, NJ. October 1990.
4. Hazardous Substance Database (HSDB): 1,1,1-Trichloroethane. National Institutes of
Health, National Library of Medicine, Bethesda, MD. 1990.
5. Sax, Irving N. and Richard J. Lewis, Sr., Dangerous Properties of Industrial Materials.
Volume III. Seventh Edition. Van Nostrand Reinhold, New York, NY. p. 3327. 1989.
6. The Merck Index, Tenth Edition. Merck Co., Inc., Rahway, NJ. p. 1377. 1983.
7. Weast, R.C., ed., CRC Handbook of Chemistry and Physics, Sixty-Ninth Edition. CRC
Press, Inc., Boca Raton, FL. p. C-266. 1988.
8. Chiou, C.T., Peters, L.J., and Freed, V.H, "A Physical Concept of Soil-Water Equilibria
forNonionic Organic Compounds," Science 206: 831-832. 1979.
9. "C2 Chlorinated Solvents," Chemical and Economics Handbook. SRI International, Menlo
Park, CA. December 1988.
10. Personal communication with R. Sherwood, Pope and Talbot Pulp, Inc., Halsey, Oregon,
by B. McMinn, TRC Environmental Corporation. "TRI Emissions of Methyl Chloroform."
June 22, 1992.
11. Memorandum from M. A. Callahan, U.S. Environmental Protection Agency, to E.
Anderson, U.S. Environmental Protection Agency. Public Docket A-84-41, II-B-1. Draft
Exposure Assessment for TSPC Solvents.
12. Howard, Philip H., ed., Handbook of Environmental Fate and Exposure Data for Organic
Chemicals, Volume II, Solvents. Lewis Publishers, Chelsea, MI. pp. 450-460. 1990.
13. U.S. Environmental Protection Agency. Health Assessment Document for 1,1,1-
Trichloroethane (Methyl Chloroform). EPA-600/8-82-003f Office of Health and
Environmental Assessment. Washington DC. 1984.
3-10
-------
14. Sheiman, Deborah A., et al., A Who's Who of American Ozone Depleters: A Guide to
3,014 Factories Emitting Three Ozone-Depleting Chemicals. Natural Resources Defense
Council. January 1990.
15. U.S. Environmental Protection Agency. 40 CFR 82, "Protection of Stratospheric Ozone;
Final Rule," Federal Register, July 30, 1992.
16. U.S. Environmental Protection Agency. 40 CFR 82, "Protection of Stratospheric Ozone,"
Federal Register, December 30, 1991.
17. United Nations Environment Programme. Handbook for the Montreal Protocol on
Substances that Deplete the Ozone Layer. Ozone Secretariat. Narobi, Kenya. May 1991.
18. Public Law 101-549. The Clean Air Act Amendments of 1990, Title VI - Stratospheric
Ozone Protection. November 15, 1990.
19. "Chemical Profile: 1,1,1-Trichloroethane," Chemical Marketing Reporter. January 27,
1992.
20. Toxic Chemical Release Inventory (TRI). 1990.
3-11
-------
SECTION 4.0
EMISSIONS FROM METHYL CHLOROFORM PRODUCTION
Methyl chloroform production and the associated air emissions are described in this
section. Process flow diagrams are included where appropriate, with specific streams or vents
in the figures labeled to correspond with the discussion in the text. Emission factors for the
production processes are presented when available, and control technologies are described. If a
particular facility is being included in an inventory, the reader is encouraged to contact the
specific facility to verify the nature of the process used, production volume, and control
technologies that are in place before applying any of the emission factors presented in this
document.
Methyl chloroform is currently produced by three companies at three plants in the United
States. The production locations and capacities are presented in Table 4-1. In 1992, the total
annual capacity for all methyl chloroform manufacturing facilities was estimated at 477 million
kgs (1,050 million Ibs) per year.1 In 1989, methyl chloroform production was 356 million kgs
(783 million Ibs).2 Total production for 1992 is expected to be approximately 273 million kgs
(600 million Ibs), about 57 percent of available capacity. With the production and consumption
phase-out required by Title VI of the 1990 Clean Air Act Amendments and the Montreal
Protocol, demand for methyl chloroform should decrease by 11.6 percent per year through 1996,
at which time demand is expected to be 165 million kgs (367 million Ibs).1 The 1990 CAAA
mandate that new production of methyl chloroform be phased out by 2002. Effective January
1, 1991, an excise tax of 13.7 cents per pound was imposed on first time sales of methyl
chloroform. The tax will gradually rise to 31 cents per pound by 1995.2 Table 4-2 shows
historical and projected figures for methyl chloroform capacity, production, imports, exports, and
demand.
4-1
-------
TABLE 4-1.
METHYL CHLOROFORM PRODUCTION LOCATIONS AND
CAPACITIES
Facility
Dow Chemical Corporation
PPG Industries
Vulcan Materials Company
TOTAL
Location
Freeport, TX
Lake Charles, LA
Geismar, LA
1992 Capacity
millions of kilograms
(millions of pounds)
227 (500)
159 (350)
91 (200)
477 (1,050)
Source: Reference 1.
NOTE: This listing is subject to change as market conditions change, facility
ownership changes, plants are closed, etc. The reader should verify the existence of
particular facilities by consulting current listings and/or the plants themselves. The
level of methyl chloroform emissions from any given facility is a function of variables
such as capacity, throughput, and control measures, and should be determined through
direct contacts with plant personnel. These operating plants and locations were current
as of January 1992.
4.1 PRODUCTION PROCESS DESCRIPTIONS
Methyl chloroform may be produced by several different processes. However, the only
method that is presently used in the United States involves the hydrochlorination of vinyl
chloride. Two additional production methods (hydrochlorination of vinylidene chloride and
chlorination of ethane) are included in the following sections for informational purposes.
4-2
-------
TABLE 4-2.
ESTIMATED DOMESTIC U.S. SUPPLY AND DEMAND OF METHYL CHLOROFORM3
Millions of kilograms (millions of pounds)
Capacity
Production
Imports
Exports
Demand
1980
434 (955)
315 (692)
None
28 (61)
287 (631)
1985
455 (1000)
268 (590)
6(13)
18 (40)
256 (563)
1986
477(1050)
296 (652)
5(12)
39 (87)
262 (577)
1987
477 (1050)
315 (694)
8(17)
50 (110)
273 (601)
1988
477 (1050)
329 (724)
10 (22)
43 (95)
296 (651)
1989
477 (1050)
356 (783)
13 (28)
56 (124)
312 (687)
1990
477 (1050)
365 (803)
4(8b)
56 (123b)
293 (645b)
1991
477 (1050)
295 (649)
None
None
None
1992
477 (1050)
273 (600C)
None
None
282 (620b)
Exports were reported by the USITC after 1978. Imports were reported for the first time in 1989 by the U.S. Government.
Imports indicated above for years prior to 1989 are based on trade estimates. Production of 395 million kgs (869 million
Ibs) as reported by the USITC for 1985 was probably erroneously high and has been more realistically estimated at 268
million kgs (590 million Ibs).
a Source: References 1, 2, 4.
b Figure is based on estimates from Reference 2.
c Figure is based on estimates from Reference 1.
-------
4.1.1 Hydrochlorination of Vinyl Chloride
The production of methyl chloroform by the hydrochlorination of vinyl chloride is a three
step process. Figure 4-1 illustrates the hydrochlorination process. The process reactions are
shown below:3
high temp
C1CH2CH2C1 > CH2CHC1 + HCl (1)
1,2-dichloroethane high press. vinyl chloride
FeCl3
CH2CHC1 + HCl > CH3CHC12 (2)
vinyl chloride 35°c (95°F) 1,1-dichloroethane
C12 (gas)
CH3CHC12 > CH3CC13 + HCl (3)
1,1-dichloroethane UV hght methyl chloroform
Reaction 1 involves the production of vinyl chloride monomer from 1,2-dichloroethane
via dehydrochlorination (not shown in Figure 4-1). 1,2-Dichloroethane is introduced into a
pyrolysis furnace where it is cracked in the vapor phase at temperatures of 450° to 620°C (842°
to 1,148°F) and pressures of 450 to 930 kPa (3.4 to 7.0 atm). The conversion of
1,2-dichloroethane to vinyl chloride approaches 50 percent. The product gas stream from the
furnace, containing vinyl chloride monomer, 1,2-dichloroethane, and hydrogen chloride, is
quenched with liquid 1,2-dichloroethane and fed to a condenser. The hydrogen chloride is
removed from the condenser in the gas phase and recovered for future use. The liquid stream
from the condenser is fed to a distillation column where it is separated into vinyl chloride
monomer product, unreacted 1,2-dichloroethane, and heavy-ends. The unreacted 1,2-
dichloroethane is recycled either to the quench column or to the finishing section of a 1,2-
dichloroethane plant.5 The vinyl chloride product is then either sold to a facility that
manufactures methyl chloroform, or, in the case of the Lake Charles PPG facility, the vinyl
chloride monomer is routed to the section of the plant that manufactures methyl chloroform.2'6
4-4
-------
HCI
j
Vinyl Chloride
Loading
\
1
r"
/
,
^^
©
i
FeClj
Catalyst
(T)
— f^\ Hydrogen Chloride + Dichloroeth
' \_y "*" Trtchloroethane to Recycle
r
s^~ ~~~x
Ai ^-x
t ®
r^
Distillation
Column
©
*•-
Vinyl Chloride
Storage
Hydro-
chlorinatlon
Reactor
Spent
Catalyst
Filter
Dlchloroethane
Trtchloroethane
Hydrogen Chloride
Light-Ends
Distillation
Column
NHs
i Wests
Cataly
Tor
Waste
Catalyst
Inter-
mediate
Storage
Hydrogen
Chlorfda
Column
\HCI
/ Low Boiling Orgai
4A
mice
J-T
Purified Methyl Chloroform
Methyl Chloroform
Distillation
Column
Stabilizer
Product
Storage
Chlorlnatlon
Reactor
©
Chlorine
Loading
1,1.2 — trlchloroethane
A
I
Denotes Potential Location
of Emission Source
Process Vent Discharge
Storage Losses
Loading Losses
Figure 4-1. Process flow diagram for the hyclrochlorination of vinyl chloride.5
-------
Reaction 2 involves the production of the intermediate 1,1-dichloroethane via the
hydrochlorination process. Vinyl chloride (Stream 1 in Figure 4-1) and hydrogen chloride
(Stream 2) are combined with recycled hydrogen chloride, recycled methyl chloroform, and
recycled dichloroethane (Stream 7) and fed to a hydrochlorination reactor. Catalytic conversion
occurs in the presence of a ferric chloride catalyst at approximately 35°C (95°F).4'5'7 Ammonia
(Stream 4) is added to the reactor effluent (Stream 3) forming a solid complex with the residual
hydrogen chloride and the ferric acid catalyst. The complex is removed by the spent catalyst
filter as a semisolid waste stream. The filtered hydrocarbon stream (Stream 5) passes to the
heavy-ends distillation column, where high-boiling chlorinated organics (tars) are removed as a
waste stream from the bottom.5'8
The overhead (Stream 6) passes to the light-ends distillation column, where a separation
is made between 1,1-dichloroethane and the lighter components, primarily unreacted vinyl
chloride. The overhead stream (Stream 7) is recycled to the hydrochlorination reactor. The 1,1-
dichloroethane product is removed as the bottom stream (Stream 8) and transferred to
intermediate storage or directly to the chlorination reactor.5'8'9
The third reaction begins when 1,1-dichloroethane from intermediate storage, or the light-
ends column, and chlorine (Stream 9) are combined and fed to the chlorination reactor, where
the 1,1-dichloroethane is converted to methyl chloroform. The reaction is exothermic,
noncatalytic and occurs at a temperature of about 400°C (752°F). The reactor product (Stream
10), crude methyl chloroform, passes to the hydrogen chloride column where the hydrogen
chloride formed in the reaction and some low-boiling organic compounds are removed
(Stream 11). This stream may be used to supply the hydrogen chloride requirements of other
chlorinated organic processes directly (e.g., the 1,2-dichloroethane process) or it may be purified
to remove the contained organics before the stream is used.5'8
The bottom stream (Stream 12) from the hydrogen chloride column passes to the methyl
chloroform column. The purified methyl chloroform product (Stream 13) is removed overhead,
stabilized, and transferred to storage. The bottom stream (Stream 14) from the methyl
4-6
-------
chloroform column (primarily 1,1,2-trichloroethane) is transferred as feed to other chlorinated
organic processes (e.g., perchloroethylene or trichloroethylene).5 Yields of methyl chloroform
from this process exceed 95 percent.8
4.1.2 Hydrochlorination of Vinylidene Chloride
In 1975, the production of methyl chloroform by the hydrochlorination of vinylidene
chloride accounted for approximately 20 percent of total methyl chloroform production.8
Although this process is no longer used for the United States, it is used in Europe and Japan and
is included in this document as a reference. The following reactions show a simplified version
of the chlorination process.8'10
C1CH2CHC12 > CH2CC12 + HC1
1,1,2-trichloroethane dehydrochlorination vinylidene chloride
FeCl3
CH2CC12 + HC1 > CH3CC13
vinylidene chloride methyl chloroform
The reaction of vinylidene chloride with the evolved hydrogen chloride yields methyl chloroform.
This reaction is carried out at approximately 30°C (86°F) under slightly superatmospheric
pressure in the presence of a catalyst such as ferric chloride. Methyl chloroform is continuously
withdrawn from the hydrochlorination step and is purified by fractional distillation. If methyl
chloroform is to be sold as a product, it is desiccated to remove moisture and stabilized to make
it suitable for commercial use. Yields of methyl chloroform from this process exceed
98 percent.4
4.1.3 Noncatalytic Chlorination of Ethane
Like the hydrochlorination of vinylidene chloride, the ethane chlorination process is no
longer used in the United States but is used in Europe and Japan. The Vulcan Materials
Company in Geismar, Louisiana operated a 31.8 million kgs (70 million Ibs) per year ethane-
4-7
-------
based production facility until 1979, when the facility converted to producing methyl chloroform
via hydrochlorination of vinyl chloride.7 The reader is directed to the documents referenced at
the end of this section for a process flow diagram.5
The chlorination of ethane yields several products and by-products including methyl
chloroform and minor quantities of 1,2-dichloroethane and 1,1,2-trichloroethane. The ethane
chlorination process includes the following reactions:5
CH3CH3
ethane
+ Cl,
A
—>
CH3CH2C1
ethyl chloride
+ HC1
hydrogen chloride
CH3CH2C1 + C12 -—> CH3CHC12 + HC1
ethyl chloride 1,1-dichloroethane
A
CH3CH2C1 > CH2CH2 + HC1
ethyl ene
A
CH3CHC12 + C12 -—> CH3CC13 + HC1
1,1-dichloroethane methyl chloroform
A
CH3CHC12 > CH2CHC1 + HC1
vinyl chloride
A
CH3CC13 > CH2CC12 + HC1
vinylidene chloride
The raw material ratios and reactor conditions determine the relative proportions of methyl
chloroform and by-products produced. If methyl chloroform is the only product desired, the
by-product chloroethane and 1,1-dichloroethane can be recycled to the chlorination reactor. Vinyl
chloride, an additional by-product, can be catalytically hydrochlorinated to yield
1,1-dichloroethane and methyl chloroform, respectively according to the following reactions.5
4-8
-------
FeCl3
CH2CHC1 + HC1 > CH3CHC12
vinyl chloride 1,1-dichloroethane
FeCl3
1,1-dichlorethane methyl chloroform
CH2CC12 + HC1 > CH3CC13
The noncatalytic chlorination of ethane process begins with the recycle and conversion
of by-product chlorinated species, including vinylidene chloride, to form methyl chloroform.5
Chlorine and ethane are fed to the chlorination reactor along with recycle streams of
1,1-dichloroethane and chloroethane. The reactor is operated adiabatically, (i.e., the heat flow
between the reactor and its surroundings is zero) with a residence time of about 15 seconds, and
is maintained at a pressure of about 600 kPa (5.9 atm) and an average temperature of about
400°C (752°F).5
The reactor exit stream is a gas containing ethane, ethylene, vinyl chloride, chloroethane,
vinylidene chloride, 1,1-dichloroethane, 1,2-di chloroethane, 1,1,2-tri chloroethane, methyl
chloroform, hydrogen chloride, and minor amounts of other chlorinated hydrocarbons. This
stream enters a quench column, where it is cooled, and a residue comprising mainly
tetrachloroethanes and hexachloroethane is removed.5
The overhead stream from the quench column is fed to a hydrogen chloride column, in
which ethane, ethylene, and HC1 are removed from chlorinated hydrocarbons. A portion of the
overheads containing HC1 is used to provide the HC1 requirements for vinylidene chloride and
vinyl chloride hydrochlorination in a later step. The remainder is purified for use in other
processes.5
The bottoms from the HC1 column containing chlorinated hydrocarbons are fed to a heavy
ends column, where a bottoms stream, mainly comprised of 1,2-di chloroethane and
1,1,2-tri chloroethane, is removed for use in other processes. Overheads from the heavy ends
column containing methyl chloroform, vinyl chloride, vinylidene chloride, chloroethane and
4-9
-------
1,1-dichloroethane are fed to the methyl chloroform column, which removes the product as a
bottoms steam.5
Overheads from the product recovery column are fed to another column, where
1,1-dichloroethane is removed as bottoms and recycled to the chlorination reactor. Overheads
from this column, containing mainly vinyl chloride, vinylidene chloride, and chloroethane, are
fed along with the HC1 by-product stream to a hydrochlorination reactor. This reactor operates
at a temperature of about 18°C (65°F), a pressure of about 450 kPa (4.4 atm), and with ferric
chloride catalyst. Alternatively, these by-products may be used in other processes at the plant.5
The hydrochlorination reactor converts vinyl chloride and vinylidene chloride to
1,1-dichloroethane and methyl chloroform, respectively. Thus, the reactor product stream consists
of unreacted chloroethane, 1,1-dichloroethane and methyl chloroform. This product stream is
mixed with ammonia (NH3) to neutralize residual HC1 and catalyst. Spent neutralized catalyst
is removed in a filter and the product is then fed to a product recovery column. The bottoms
from this column, mostly methyl chloroform, are recycled to the methyl chloroform column.
Overheads, composed of chloroethane and 1,1-dichloroethane, are recycled to the chlorination
reactor.5
4.2 EMISSIONS
Air emissions associated with methyl chloroform production arise from loading operations,
storage, process vents, and equipment leaks. Methyl chloroform emissions from secondary
sources, such as waste treatment, are discussed in Section 6.0. Table 4-3 lists 1978 production
emissions for the three facilities currently manufacturing methyl chloroform. The table also
includes emissions for the Dow Plaquemine, Louisiana facility, which closed in the early 1980s.11
In 1978, both Dow facilities and PPG employed the hydrochlorination of vinyl chloride
production process while Vulcan made methyl chloroform by the noncatalytic chlorination of
ethane.7'12 Although the data in Table 4-3 are based on 1978 production data, current total
emissions are expected to be similar to 1978 production and capacity values which approximate
4-10
-------
TABLE 4-3.
METHYL CHLOROFORM PRODUCTION EMISSIONS
Company
Dow
Dow
PPG
Vulcan
Total
Location
Freeport, TX
Plaquemine,
LA
Lake Charles,
LA
Geismar, LA
1978
Production
in millions
of kg
(millions of Ibs)
121 (266)
73 (160)
73 (160)
15 (34)
282 (620)
1978
Capacity
in millions
of kg
(millions of Ibs)
227 (500)
136 (300)
136 (300)
29 (65)
528 (1165)
Thousands of kilograms (thousands of pounds)
Process
Emissions
42.5 (93.6)
0.0 (0.0)
52.2 (115.0)
11.2 (24.6)
105.9 (233.2)
Storage
Emissions
134.9 (295.3)
7.9 (17.4)
164.7 (363.2)
35.0 (77.2)
342.5 (753.1)
Fugitive
Emissions
59.1 (130.2)
3.4 (7.6)
72.5 (160.0)
15.4 (34.0)
150.4 (331.8)
Total
Emissions
235.5 (519.1)
11.3 (25.0)
289.6 (638.4)
61.6 (135.7)
598.0 (1,318.2)
Source: Reference 11.
-------
the projected 1992 production and capacity figures indicated in Tables 4-1 and 4.2.UU2
4.2.1 Process Emissions
Figure 4-1 illustrates that during methyl chloroform production by the hydrochlorination
of vinyl chloride, process vent discharges (A) of methyl chloroform occur primarily from the
hydrogen chloride vent and the distillation column vents. Table 4-4 presents available emission
factor estimates for methyl chloroform production. Little information was found on emission
controls.
TABLE 4-4.
METHYL CHLOROFORM EMISSION FACTORS FROM
METHYL CHLOROFORM PRODUCTION
Potential Emission Source
Condenser/Distillation Column
Distillation Col. /Incinerator Control/
Production from Ethane
Separation Unit/Production by
Hydrochlorination
Heat Transfer Unit/Production by
Hydrochlorination
Emission Factor
kg/metric ton
(Ib/ton)
0.720 (1.440)
0.003 (0.006)
0.500 (1.000)
9.000 (18.000)
Emission Factor
Rating
E
E
E
E
Note: Emission factors were developed from model plant calculations, mass balance
calculations, and testing.
Source: Reference 13.
The documents referenced at the end of this section provide discussions of potential
emission sources of methyl chloroform from the hydrochlorination of vinylidene chloride and the
noncatalytic chlorination of ethane.5
4-12
-------
4.2.2 Storage Emissions
Other possible sources of methyl chloroform emissions are storage tank losses (point B
in Figure 4-1) and handling losses (point C in Figure 4-1) that occur during product loading into
drums, tank trucks, tank cars, barges, or ships. Storage tank losses are either working losses that
occur while filling the tank, or breathing losses due to expansion from temperature changes.
These emissions are described briefly in this section. For more information, including equations
for estimating storage tank emissions, the reader is referred to the U.S. Environmental Protection
Agency's report titled Estimating Air Toxics Emissions from Organic Liquid Storage Tanks (EPA-
450/4-88-004).14
Methyl chloroform is usually stored in floating roof tanks which decrease the degree of
evaporation loss of organic liquids. There are two main types of floating roof tanks: external
and internal. External floating roof tanks consist of a cylindrical steel shell equipped with a roof
which floats on the surface of the stored liquid, rising and falling with the liquid level. The
liquid is completely covered by the floating roof, except at the small annular space between the
roof and the tank wall. A seal attached to the roof contacts the tank wall and covers the annular
space. The seal slides against the tank wall as the roof is raised or lowered. The purpose of the
floating roof and the seal is to reduce the evaporation loss of the stored liquid.14
The internal floating roof tank has both a permanent fixed roof and a floating deck inside.
The deck rises and falls with the liquid level and either rests directly on the liquid surface or
rests on pontoons several inches above the liquid level. There are two basic types of internal
floating roof tanks: tanks in which the fixed roof is supported by vertical columns within the
tank, and tanks with a self-supporting fixed roof and no internal support columns. Fixed roof
tanks that have been retrofitted to employ a floating deck are typical of the first type, while
external floating roof tanks typically have a self-supporting roof when converted to an internal
floating roof tank. These tanks are freely vented by circulation vents at the top of the fixed roof.
The vents minimize the possibility of organic vapor accumulation in concentrations approaching
the flammable range.14
4-13
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Methyl chloroform emissions from external and internal floating roof tanks are
characterized as standing storage and withdrawal losses. Standing storage losses include rim seal
loss, deck fitting loss, and deck seam loss for the internal tanks; and rim seal loss for the external
tanks. Variables needed for determining floating roof storage tank emissions include tank
parameters (e.g., height, diameter, and capacity), temperatures, and other environmental
parameters, and characteristics of the stored solvent liquid (e.g.., molecular weight and vapor
pressure).14
Standing storage loss from external floating roof tanks is the major source of evaporative
loss from solvent storage tanks. This results from wind-induced mechanisms as air flows across
the top of the external floating roof tank. These mechanisms may vary, depending upon the type
of seals used to close the annular vapor space between the floating roof and the tank wall.14
Internal floating roof tanks generally incorporate two types of primary seals that perform
by closing the annular space between the edge of the floating roof and the tank wall.
Historically, secondary seals were not commonly used with internal floating roof tanks.
However, recent regulations concerning internal floating roof tanks have led to increased use of
secondary seals. Another form of emissions from the internal floating roof tanks is through deck
fitting loss. These emissions result from penetrations in the roof by deck fittings, fixed roof
column supports, or other openings.14
Withdrawal loss is a potential source of atmospheric emissions from floating roof tanks.
Loss occurs through vaporization of the liquid that clings to the tank wall and is exposed to the
atmosphere when the floating roof lowers when liquid is withdrawn.14
In addition to residual emissions of methyl chloroform from floating roof storage tanks,
some residual emissions can occur from the handling and shipping of the chemical through the
use of tank trucks and tank cars. An emission factor of 0.605 g/kg (1.22 Ib/ton) methyl
chloroform produced was identified for evaporative loss through the handling of methyl
4-14
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chloroform.13 This emission factor has an assigned quality rating of "U." Insufficient information
is available to accurately assign a quality rating to the emission factor.
4.2.3 Equipment Leak Emissions (Fugitive Emissions)
Emissions occur from process equipment components whenever the liquid or gas streams
leak from the equipment. Equipment leaks can occur from the following components: pump
seals, process valves, compressor safety relief valves, flanges, open-ended lines, and sampling
connections. Emission estimates can be calculated in the five ways described in the EPA
publication Protocols for Generating Unit-Specific Emission Estimates for VOC and VHAP
(EPA-450/3-88-010).15 The methods differ in complexity; however, the more complex the
method, the more reliable the emission estimate.
The simplest method requires that the number of each component type be known.
Furthermore, for each component, the methyl chloroform content of the stream and the time the
component is in service are needed. This information is then multiplied by the EPA's average
emission factors for the Synthetic Organic Chemical Manufacturing Industries (SOCMI) shown
in Table 4-5.15 This method should only be used if no other data are available, as it may result
in an overestimation of actual equipment leak emissions. For each component, estimated
emissions are:
No. of
equipment
components
r Weight % r Component- r No. hrs/yr in ]
X methyl chloroform X specific X methyl chloroform
L in the stream L emission factor L service J
To obtain more accurate equipment leak emission estimates, one of the more complex
estimation methods should be used. These methods require that some level of emission
measurement for the facility's equipment components be performed. These are described briefly,
and the reader is referred to the Protocols document for the calculation details.15
The first method, the leak/no leak approach, is based on a determination of the number
of leaking and non-leaking components. These values are then multiplied by two different sets
4-15
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TABLE 4-5.
AVERAGE EMISSION FACTORS FOR FUGITIVE
EQUIPMENT LEAK EMISSIONS
Equipment
Valves
Pump Seals
Compressor Seals
Pressure Relief
Seals
Flanges
Open-Ended Lines
Sampling
Connections
Service
Gas
Light Liquid
Heavy Liquid
Light Liquid
Heavy Liquid
Gas/Vapor
Gas/Vapor
All
All
All
Emission Factor
(kg/hr/source)
0.0056
0.0071
0.00023
0.0494
0.0214
0.228
0.104
0.00083
0.0017
0.0150
Emission
Factor
(Ib/hr/source)
0.0123
0.0157
0.00051
0.1089
0.0472
0.5027
0.2293
0.0018
0.0037
0.0331
Quality
Ratinga
U
U
U
U
U
U
U
aBased on engineering judgement.
Source: Reference 15.
of EPA-derived emission factors as presented in the Protocols document.15 The second method
groups screening results into three ranges: 0-1,000 ppmv; 1,001-10,000 ppmv; and greater than
10,000 ppmv. The number of each component falling in a particular range is multiplied by the
component-specific emission factor for that range. These emission factors, like the factor for the
leak/no leak approach, have also been developed by EPA. The next method uses screening data
in correlation equations derived from earlier work by EPA.
The last procedure calls for the facility to develop its own correlation equations but
requires more rigorous testing, bagging, and analyzing of equipment leaks to determine mass
emission rates.
4-16
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Although no specific information on controls used by the industry was identified,
equipment components in methyl chloroform service will have some controls in place. Generally,
control of fugitive emissions will require the use of sealless or double mechanical seal pumps,
an inspection and maintenance program, as well as replacement of leaking valves and fittings in
conjunction with an inspection and maintenance program. Typical controls for equipment leaks
are listed in Table 4-6. Additionally, some leakless equipment is available such as leakless
valves and sealless pumps.16
4-17
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TABLE 4-6.
CONTROL TECHNIQUES AND EFFICIENCIES APPLICABLE TO
EQUIPMENT LEAK EMISSIONS
Equipment component
(Emission source)
Pump Seals:
Packed and
Mechanical
Compressors
Flanges
Valves:
Gas
Liquid
Pressure Relief Devices
Gas
Sample Connections
Open-ended Lines
Control Technique
Seal area enclosure vented to a
combustion device
Monthly LDARb
Quarterly LDAR
Semiannual LDAR
Annual LDAR
N/Ad
Vent degassing reservoir to
combustion device
None available
Monthly LDAR
Quarterly LDAR
Semiannual LDAR
Annual LDAR
Monthly LDAR
Quarterly LDAR
Semiannual LDAR
Annual LDAR
Monthly LDAR
Quarterly LDAR
Rupture Disk
Closed-purge sampling
Caps on open ends
Percent reductiona
100
61
32
0
0
100
0
73
64
50
24
59
44
22
0
50
44
100
100
100
alf a negative reduction for a control technique was indicated, zero was used.
bLDAR (Leak detection and repair).
cAssumes the seal barrier fluid is maintained at a pressure above the pump stuffing box
pressure and the system is equipped with a sensor that detects failure of the seal and/or
barrier fluid system.
dN/A (Not applicable). There are no VOC emissions reported from this component.
Source: Reference 17.
4-18
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4.3 REFERENCES FOR SECTION 4.0
1. "Chemical Profile: 1,1,1-Trichloroethane," Chemical Marketing Reporter. January 27,
1992.
2. "1,1,1-Trichloroethane," Chemical Products Synopsis, Mannsville Chemical Products,
Asbury Park, NJ. October 1990.
3. U.S. Environmental Protection Agency. Source Assessment: Chlorinated Hydrocarbons
Manufacture. EPA-600/2-79-019g. Industrial Environmental Research Laboratory.
Research Triangle Park, NC. August 1979.
4. "Chemical & Engineering News. 1992," Chemical & Engineering News 70(26). 1992.
5. U.S. Environmental Protection Agency. Organic Chemical Manufacturing, Volume 8,
Report 4, 1,1,1-Trichloroethane and Perchloroethylene, Trichloroethylene, and Vinylidene
Chloride (Abbreviated Report). EPA-450/3-80-028c. Office of Air Quality Planning and
Standards. Research Triangle Park, NC. October 1980.
6. "Vinyl Chloride," Chemical Products Synopsis, Mannsville Chemical Products, Asbury
Park, NJ. February 1991.
7. "C2 Chlorinated Solvents," Chemical and Economics Handbook, SRI International, Menlo
Park, CA. December 1988.
8. Lowenheim, F.A., and Moran, M.K. "1,1,1-Trichloroethane," Faith, Keyes, and Clark's
Industrial Chemicals, Fourth ed., pp. 836-843. 1975.
9. Air Pollution from Chlorination Processes. Processes Research, Inc. APTD 1110.
CPA 70 1. Cincinnati, OH. 172 pp. March 31, 1972.
10. U.S. Environmental Protection Agency. Health Assessment Document for 1,1,1-
Trichloroethane (Methyl Chloroform). EPA-600/8-82-003f Office of Health and
Environmental Assessment. Washington, DC. February 1984.
11. U. S. Environmental Protection Agency. Human Exposure to Atmospheric Concentrations
of Selected Chemicals, Volume II, Appendix A-18. Office of Air Quality Planning and
Standards. Research Triangle Park, NC. 1984.
12. "1,1,1-Trichloroethane," Chemical Products Synopsis, Mannsville Chemical Products,
Cortland, NY. November 1980.
4-19
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13. U.S. Environmental Protection Agency. The Crosswalk/Air Toxic Emission Factor
Database Management System, Version 1.2. Office of Air Quality Planning and Standards.
Research Triangle Park, NC. October 1991.
14. U.S. Environmental Protection Agency. Estimating Air Toxics Emissions from Organic
Liquid Storage Tanks. EPA-450/4-88-004. Office of Air Quality Planning and Standards.
Research Triangle Park, NC. October 1988.
15. U.S. Environmental Protection Agency. Protocols for Generating Unit-Specific Emission
Estimates for Equipment Leaks of VOC and VHAP. EPA-450/3-88-010. Office of Air
Quality Planning and Standards. Research Triangle Park, NC. 1988.
16. U.S. Environmental Protection Agency. Estimating Releases and Waste Treatment
Efficiencies for the Toxic Chemical Release Inventory Form. EPA-560/4-88-002. Office
of Pesticides and Toxic Substances. Washington, DC. 1987.
4-20
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SECTION 5.0
EMISSIONS FROM MAJOR USES OF METHYL CHLOROFORM
This section discusses emissions from major industrial processes that use methyl
chloroform as a solvent or a feedstock. The processes described are solvent cleaning (e.g., vapor
degreasing and cold cleaning) operations, paint and ink manufacturing, aerosol manufacturing,
adhesive manufacturing, production of hydrochlorofluorocarbons (HCFC), including
hydrochlorofluorocarbon 142b (HCFC-142b) and hydrochlorofluorocarbon 141b (HCFC-141b),
and miscellaneous uses.1 In addition, product and process descriptions are provided for uses of
methyl chloroform in solvent applications. The application of methyl chloroform-containing
paints, coatings, and inks is discussed in Section 6.0. Because of limited application information,
the manufacture and application of aerosols and adhesives containing methyl chloroform is
discussed in this section. Process flow diagrams are included as appropriate, with specific
streams or vents in the figures labeled to correspond with the discussion in the text.
Emissions of methyl chloroform are expected from all facilities involved in the previously
mentioned operations. However, insufficient information is available to develop emission factors
for fugitives or process emission sources. Any available information is provided in each
subsection. The reader is encouraged to contact the Toxic Chemical Release Inventory and
specific production facilities for information on methyl chloroform emissions and control
technologies. It should be noted, however, that TRI emission estimates may be based upon
engineering estimates, may include accidental emission releases, and may not be reliable.
Residual emissions from methyl chloroform-containing materials are discussed separately
in Section 6.0. Methyl chloroform emissions produced as a result of a chemical reaction (by-
product emissions) are also discussed in Section 6.0.
5-1
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5.1 SOLVENT CLEANING
The first commercial success of methyl chloroform was as a replacement for carbon
tetrachloride in room temperature, metal cleaning operations.1 Cleaning operations, including
cold cleaning and vapor degreasing, remain the largest end use of methyl chloroform.2'3 Methyl
chloroform is the most widely used and the most cost-effective chlorinated solvent.2'4 Domestic
production and demand for methyl chloroform exceeds demands for other chlorinated solvents,
such as perchloroethylene (PCE), trichloroethylene (TCE), and methylene chloride. Although
terpenes, aqueous cleaners, and organic surfactants are being used as replacements for methyl
chloroform in some cleaning applications because of the restrictions required under the Montreal
Protocol and the 1990 Clean Air Act Amendments, there is no direct replacement for methyl
chloroform in other cleaning applications.2'3
Methyl chloroform will dissolve oils, greases, waxes, tars, fats, gums, and resins, yet it
will not attack or harm most plastics and elastomers. Methyl chloroform is the preferred solvent
for the cleaning of electronic components, electrical parts, and printed circuit boards where other
solvents may damage the insulation or cause heat warping. It is also used in metal cleaning and
in maintenance cleaning of products such as aircraft, automobiles, diesel engines, electric motors,
generators, and compressed gas cylinders.2'4 The five two-digit SIC groups that use the largest
amount of methyl chloroform for cleaning are as follows: SIC 25 (furniture and fixtures), SIC
34 (fabricated metal products), SIC 36 (electric and electronic equipment), SIC 37 (transportation
equipment) and SIC 39 (miscellaneous manufacturing industries). Other industries that use
methyl chloroform in cleaning operations include SIC 20 (food and kindred products), SIC 33
(primary metals), SIC 35 (nonelectric machinery), and SIC 38 (instruments and clocks). Non-
manufacturing industries (e.g., railroad, bus, aircraft, and truck maintenance facilities), automotive
and electric tool repair shops, automobile dealers, and service stations also use methyl chloroform
in cleaning operations.5'6
5-2
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Methyl chloroform exhibits chemical instability when exposed to the severe conditions
(i.e.., high temperatures, metals, or metal salts) encountered in vapor degreasing or other cleaning
operations. For this reason, methyl chloroform normally contains up to five percent stabilizer
to prevent decomposition. If the level of stabilizer falls below a certain level, methyl chloroform
may hydrolyze.2'4 Methyl chloroform is not normally used with aluminum products unless
suitable quantities of stabilizer are present. Uninhibited (unstabilized) methyl chloroform may
react with aluminum to produce aluminum chloride; 2,2,3,3-tetrachlorobutane;
1,1-dichloroethylene; and hydrogen chloride. Adequate metal inhibitors can prevent methyl
chloroform-aluminum reactivity and allow the solvent to be used in aluminum metal-cleaning
applications.7 A discussion of stabilizers is included in Section 3.0.
Many of the facilities that employ metal cleaning operations are small (employing less
than 50 people), and, therefore do not purchase methyl chloroform directly from the
manufacturing facilities listed in Table 4-1. It is estimated that 80 to 85 percent of the
chlorinated solvent (i.e., methyl chloroform, methylene chloride, PCE, and TCE) sales to users
are handled through distributors. The largest distributors of chlorinated solvents in the United
States are Van Waters & Rogers, Ashland Chemical, ChemCentral, Thompson-Hay ward, and
Union Chemicals.4
5.1.1 Process Description
Solvent cleaners can be divided into three main categories: cold cleaners, open-top vapor
cleaners (OTVC), and conveyorized (often called in-line) cleaners. Although most in-line
cleaners are vapor degreasers, some are cold cleaners. In 1987, an estimated 150 million kgs
(330 million Ibs) of chlorinated solvent were used by OTVC; 50 million kgs (110 million Ibs)
by in-line vapor cleaners; 30 million kgs (66 million Ibs) by in-line cold cleaners; and 2 million
kgs (4.4 million Ibs) by other cold cleaners.5 The 1992 methyl chloroform consumption estimates
for OTVC were the same as the 1987 figures, while estimates for cold cleaners decreased by 2.27
million kgs (5 million Ibs).4
5-3
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Spraying, brushing, flushing, and immersion are cleaning techniques used with cold
cleaners.5 However, methyl chloroform is not a widely used cold cleaning solvent. The major
cold cleaner manufacturers indicate that none of them currently sells or have recently sold units
for use with solvents other than methylene chloride and nonhalogenated solvents. Although there
may be some older units that use other chlorinated solvents, the total number of these units
nationwide is negligible.8
Open top vapor cleaners are used primarily in metalworking operations and other
manufacturing facilities. They are seldom used for ordinary maintenance cleaning because cold
cleaners using petroleum distillate solvents can usually perform this type of cleaning at a lower
cost. Exceptions applying to the use of methyl chloroform include maintenance cleaning of
electronic components, small equipment parts, aircraft parts, and other miscellaneous parts that
require a high degree of cleanliness.5
A typical OTVC consists of a tank equipped with a heating system (e.g., steam,
electricity, or fuel combustion) and cooling coils.9 Heating elements on the inside bottom of the
tank raise the temperature of the solvent to its boiling point, creating vapor. The cooling coils
located on the inside perimeter of the tank above the liquid level condense the solvent vapors,
creating a controlled vapor zone which prevents vapors from escaping from the tank. The parts
to be cleaned are lowered into the vapor zone where solvent condenses on their surfaces and
dissolves the adhering dirts and oils.5'8 Additional cleaning action can occur if the parts are
lowered into the solvent bath or are sprayed with the solvent prior to the condensation phase.
Once thoroughly cleaned, the parts are removed from the tank and dried. Nearly all vapor
degreasers are equipped with a water separator that collects the condensate (containing both water
moisture and condensed solvent) and separates it into its organic and aqueous phases. The water
phase is removed while the condensed solvent is fed back into the solvent bath of the vapor
degreaser.10
5-4
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In-line cleaners feature automated conveying systems for continuous cleaning of parts.
Most in-line cleaners use vapor cleaning rather than cold cleaning as their cleaning mechanism.
In-line cleaners use the same cleaning techniques as OTVC, but operate on a larger scale in an
automated, conveyorized fashion.5'8 The five main types of in-line cleaners using chlorinated
solvents include cross-rod, monorail, belt, strip, and printed circuit board processing equipment
(e.g., photoresist strippers, flux cleaners, and developers). The photoresist stripper, a device used
in printed circuit board processing, is typically the only in-line cleaner that employs cold
cleaning. Although in-line cleaners tend to be the largest of the three types of solvent cleaners,
they emit less solvent per part cleaned because they are usually enclosed systems.5
5.1.2 Emissions
Solvent evaporation occurs both directly and indirectly with all types of solvent cleaning
equipment. Major causes of emissions include the loss of solvent vapor from the cleaning tank
due to diffusion and convection. Diffusion (e.g., evaporation from liquid solvent in a cold
cleaner) or convection (e.g., evaporation from liquid solvent induced by warm freeboards) occurs
during idling at the air/solvent vapor interface. The freeboard ratio is an index for freeboard
height and is equal to the freeboard height divided by the cleaner width. Evaporation of solvent
also occurs as parts are introduced or extracted (i.e., drag out) during the cleaning process or
when parts are spray cleaned. These evaporative losses are referred to as workload losses.5'8
Other potentially significant losses that contribute to the total solvent emissions from a solvent
cleaner include filling/draining losses, wastewater losses, start-up/shutdown losses, downtime
losses, and losses from leaks from the cleaning mechanism of associated equipment. In addition,
losses occur from solvent storage and solvent transfer.5 The quantity of emissions varies
depending on the type, design, and size of the cleaner, the hours of operation, operating
techniques, and the type of material being cleaned. Because emissions are ultimately a function
of solvent use, techniques and practices designed to conserve solvent use are beneficial in
reducing atmospheric emissions.5'8
5-5
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Potential control methods for organic solvent cleaners include add-on equipment and
improved operating practices. Add-on equipment can be as simple as adding covers to equipment
openings, enclosing equipment, increasing freeboard height, adding freeboard refrigeration
devices, and using automated parts handling systems. The freeboard height is the distance from
the liquid solvent surface or top of the vapor to the lip of the tank. Increasing the freeboard
height decreases drafts, and thereby solvent diffusion, within the cleaner. These devices limit
diffusional and convective losses from solvent tanks and evaporative losses due to solvent carry-
out. More sophisticated control techniques include carbon adsorption systems to recover solvent
vapors.8
Improved operating practices may limit emissions from solvent cleaning. These
improvements, characterized by practices that reduce solvent exposure to the atmosphere, include
minimizing open surface area, keeping cleaner covers closed, fully draining parts prior to removal
from cleaner, maintaining moderate conveyor speeds, keeping ventilation rates moderate, using
a coarse spray or solid stream of solvent instead of a fine spray, not using compressed air sprays
to blow-dry parts or to mix cleaning baths, and by placing wipe rags in a closed container and
reusing them whenever possible. The emission reductions achievable through the use of control
devices vary depending on the operating schedule of the machine.
In vapor cleaning, improper heat balance, air currents, high water content, and solvent
degradation are the primary factors affecting solvent losses, necessitating greater virgin solvent
use. Equipment configurations and operational practices that abate the problems will be useful
in reducing potential solvent emissions from vapor cleaning. Conservation practices for vapor
cleaners as recommended by a major cleaning solvent manufacturer are summarized below.8
1. Use least amount of heat necessary to keep solvent at a boil and provide adequate vapor
production.
2. Regulate cooling level by water temperature or flow rate adjustments.
3. Monitor water jacket temperature and flow rate to prevent migration of hot solvent vapor
up cleaner side walls.
5-6
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4. Use cold coil traps to lessen vapor losses.
5. Use covers, especially during idle periods, on open-top cleaners.
6. Avoid drafts over the cleaner by locating the unit to minimize natural drafts or use baffles
to prevent vapors from being disturbed.
7. Extend the freeboard height of the cleaner.
8. Spray in the vapor zone of the cleaner to minimize the generation of a vapor-air mixture
and the disruption of the vapor interface.
9. Use minimum exhaust velocity necessary to provide proper vapor control in the work
area.
10. Arrange air movement in the room to minimize wind tunnel effects.
11. Avoid rapid parts or basket movement in the vapor zone.
12. Minimize the level of dissolved water in the solvent.
13. Minimize the introduction of water to prevent the depletion of solvent stabilizers.
14. Have a separate water trough for refrigerated coils.
15. Minimize and remove visible signs of corrosion to minimize solvent decomposition.
16. Monitor and maintain solvent stabilizers, inhibitors, and acid acceptors.
17. Remove metal parts, fines, and sludge to prevent stabilizer depletion and resulting solvent
decomposition.
18. Avoid high oil concentration build-up.
19. Minimize solvent carry-out on parts.
20. Bring parts to vapor temperature prior to removal to minimize dragout.
21. Do not overload the cleaning capacity of the cleaner.
22. Use properly sized baskets in the cleaner to reduce vapor-air mixing.
23. Do not expose heating coils to solvent vapor.
5-7
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24. Use only clean or non-porous materials in the cleaning process.
25. Operate a cleaner leak detection and repair program.
Tables 5-1 and 5-2 present available emission factor data for methyl chloroform emissions
from OTVC solvent cleaners. A more detailed description of emissions is available from the
EPA document Alternative Control Technology Document - Halogenated Solvent Cleaners (EPA-
450/3-89-030) and the solvent degreasing project file in the Office of Air Quality Planning and
Standards, Research Triangle Park, North Carolina.5 Information in the project file was
unavailable at the time of document preparation.
TABLE 5-1.
SUMMARY OF EMISSIONS TESTS ON IDLING OTVC
(USING METHYL CHLOROFORM AS SOLVENT)
Primary Condenser
Temperature
in °C (°F)
10 (50)
21 (70)
29 (84)
Emission Rateb
kg/m2/hr
(Ib/ft2/hr)
0.425 (0.087)
0.586 (0.120)
0.698 (0.143)
Rating
C
C
C
a FBR (freeboard ratio).
b Emissions are based on a 0.9 m2 Auto-Sonics Cleaner with a FBR = 0.7.
Source: Reference 8.
5.2 PAINT AND INK MANUFACTURING
Methyl chloroform is one solvent used as a raw material in the manufacture of paints and
inks. It can be blended with slow or medium evaporating solvents to achieve the flow, leveling,
and application properties required by paint and ink formulators. Methyl chloroform exhibits
-------
TABLE 5-2.
SUMMARY OF EMISSIONS TESTS ON WORKING OTVC (USING METHYL
CHLOROFORM AS SOLVENT)
Conditions
Cleaner Size
(m2)
1.8
1.8
1.8
1.4
0.9
0.9
0.9
0.4
0.4
Cleaner Make
Detrex
Detrex
Detrex
Auto-Sonics
Auto-Sonics
Auto-Sonics
Auto-Sonics
Auto-Sonics
Auto-Sonics
Air Speed
(FPM)
calm
130
160
b
b
__b
b
30
30
Primary
Condenser
Temperature
in °C (°F)
b
__b
b
b
10 (50)
21 (70)
29 (84)
21 (70)
21 (70)
FBRa
0.75
0.75
0.75
b
b
__b
b
0.75
1.0
Emission Rate
kg/m2/hr
(Ib/ft2/hr)
0.483 (0.099)
0.845 (0.173)
1.138 (0.233)
0.308 (0.063)
0.488 (0.100)
0.684 (0.140)
0.830 (0.170)
0.547 (0.112)
0.449 (0.092)
Rating
C
C
C
D
C
C
C
C
C
aFBR (freeboard ratio). The freeboard ratio is an index for freeboard height and is equal to the freeboard height divided
by the cleaner width. The freeboard height is the distance from the liquid solvent surface or top of the vapor to the lip
of the tank. Increasing the freeboard height decreases drafts, and thereby solvent diffusion, within the cleaner.
"Working" emissions include diffusion, convection, and workload losses (but not leaks, solvent transfer losses or downtime
losses).
blnformation unknown or not available.
Source: Reference 8.
-------
resin solubility, nonflammability, and provides enhanced cleaning ability (which leads to
improved paint adhesion on the substrate).6 Because methyl chloroform has been determined by
the EPA to be of negligible photochemical reactivity, it has been used as a substitute for solvents
(e.g., some aliphatic and aromatics) in traditionally high VOC coating formulations. The use of
methyl chloroform has enabled many coating manufacturers to meet current governmental health,
safety, and environmental regulations.12
In 1989, 10.2 million kgs (22.5 million Ibs) of methyl chloroform were consumed in
paints and coatings (SIC 2851).12 An additional 14.7 million kilograms (32.3 million Ibs) of
methyl chloroform are estimated to be consumed in inks. Consumption in paints and inks
accounts for approximately seven percent of total methyl chloroform end uses.3 The largest use
of methyl chloroform in coatings is in air drying paints such as traffic paints and aerosol cans.
Section 6.1 discusses the application of methyl chloroform-containing paints (surface coating).
Paints and inks are made by blending pigments, solvents, resins (or binders), oils (for
some inks), and other additives. The fluid component of the paint or ink, made of binders (oils
and/or resins) and solvents, is called the vehicle. Vehicles transfer the pigment/binder mixture
to a surface in a thin, uniform film and normally play no role in film formation. When a paint
or ink is deposited on a substrate, the vehicle solvent(s) should evaporate completely. (In the
case of reactive diluents and two- and three-component coatings, a portion of the vehicle becomes
part of the coating film.) Methyl chloroform is only one of the vehicle solvents used by paint
and ink manufacturers.13
In 1987, Paint and Allied Products facilities (SIC 2851) were composed of 1,123
companies operating 1,426 plants, two-thirds of which were located in 10 states. The 1987
Census of Manufacturers reports that the 504 ink manufacturing facilities in the United States
(SIC 2893) are owned by 224 companies which employ a total of 11,100 people in nineteen
States and the District of Columbia. Over 50 percent of paint manufacturing plants and 60
percent of ink manufacturing facilities are small, employing fewer than 20 people and
specializing in a limited product line marketed within a small geographic region.13 Ward's
5-10
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Business Directory lists 364 paint and allied products facilities in SIC 2851 with 1990 sales
greater than $1,000,000. Ward's also lists 56 ink manufacturing facilities in SIC 2893 with 1990
sales greater than $1,000,000.14 These lists are provided in Appendix B, Table B-l and
Table B-2.
One method used to categorize the products of the paint manufacturing industry is by end-
use (e.g., markets served). The use categories are architectural coatings, product coatings for
original equipment manufacturers (OEM), and special purpose coatings. A summary of
chlorinated solvents consumption in the paint use divisions by use category and subcategory is
found in Table 5-3. Methyl chloroform accounts for 35 to 40 percent of the chlorinated solvents
used in paints and coatings.12
No specific information was available providing the amount of methyl chloroform
consumed in inks. However, methyl chloroform (and other organic solvents) are most often used
in inks that employ a solvent carrier such as flexographic and gravure inks.4 The other two
primary ink classifications, letterpress, and lithographic and offset inks, are of an oil or paste base
and are considered to be minor emission sources.13
5.2.1 Process Description
Paint and ink facilities use similar manufacturing processes to produce their respective
products in batch scale production fashion. Most small plants (i.e., facilities employing less than
20 people) produce paint in 40 to 2,000 liter (10 to 528 gallon) batches, while larger facilities
produce paint in 800 to 11,000 liter (211 to 2,906 gallon) batches with stock items made in
40,000 liter (10,568 gallon) runs. Inks are produced in batches ranging from 4 liters to over
4,000 liters (1 to 1,057 gallons).13
5-11
-------
TABLE 5-3.
ESTIMATED CONSUMPTION OF SOLVENTS IN PAINTS AND COATINGS,
BY MARKET
Coating Market
Product OEM Coatings (TOTAL)
Miscellaneous Product Finishes
Architectural Coatings (TOTAL)
Special Purpose Coatings (TOTAL)
Traffic Paints
Aerosols
Thinner and Miscellaneous
TOTAL PAINTS AND
COATINGS
Total Solvent Consumption
millions of kilograms
(millions of pounds)
1988
633 (1,396)
116 (256)
283 (624)
298 (657)
59 (130)
42 (93)
488 (1,076)
1,919 (4,232)
1989
635 (1,400)
116 (256)
276 (608)
300 (661)
59 (130)
42 (93)
764 (1,684)
2,192 (4,832)
Chlorinated Solvent Consumption
millions of kilograms
(millions of pounds)
1988
2.7 (6.1)
2.7 (6.1)
0
9.5 (21)
5.5 (12.2)
4 (8.9)
10.4 (23)
34.8 (77.3)
1989
2.8 (6.2)
2.8 (6.2)
0
9.5 (21)
5.5 (12.2)
4 (8.9)
10.4 (23)
35.0 (77.5)
to
Note: Totals may not add due to rounding.
Source: Reference 12.
-------
In most cases, manufacturing facilities purchase raw materials (e.g., pigments, solvents,
resins, and other additives) and then formulate, or blend, a finished product. Normally, no
chemical reactions take place during the process. Batch process production of paint and ink
involves four major steps:
preassembly and premix
• pigment grinding/milling
product finishing/blending
product filling/packaging
The manufacturing process is summarized in Figure 5-1.13
The first step in the manufacturing process is preassembly and premix. In this step, the
liquid raw materials (e.g., resins, solvents, oils, alcohols, and/or water) are "assembled" and
mixed in containers to form a viscous material to which pigments are added. The premix stage
results in the formation of an intermediate product which is referred to as the base or mill base.
With further processing, this base with high pigment concentration may become any one of a
variety of specific end products.13
The incorporation of the pigment into the paint or ink vehicle to yield a fine particle
dispersion is referred to as pigment grinding or milling. The goal of pigment grinding is to
achieve fine, uniformly-ground, smooth, round pigment particles which are permanently separated
from other pigment particles. The degree to which this is realized determines the coating
effectiveness and permanency of the paint or ink. Some of the more commonly used types of
dispersion (milling) equipment are roller mills, ball and pebble mills, attritors, sand mills, bead
and shot mills, high-speed stone and colloid mills, high-speed disk dispersers, impingement mills,
and horizontal media mills.13
Final product specifications are achieved in the product finishing step which consists of
three intermediate stages: thinning, tinting and blending. Material letdown, or thinning, is the
process by which a completed mill base dispersion is let down or reduced with solvent and/or
binder to give a coating which is designed to provide a durable, serviceable film that is easily
5-13
-------
Solvents Reactants
E £ 2
1 S I 3
a. a: (/> <
c c 5> :p
.1 'S I 1
a. o: to <
Large Scale Facility
Onsite Resin Production
1
!••
P a
i i
Resin
Production
: S
3 1
; en
'
1 L"
'III
Preassembly
and
Premix
"1
Pigment
Grinding
or Milling
(Continuous
Operations)
> 1 1
\l/ \l/
-tllll
Product
nnlshing
1
Rlter
^
nil
Shipment
Container
Sources of VOC Emissions
A — Emissions directly to air
Figure 5-1. Flow diagram of the paint and ink manufacturing process.13
-------
applied to the substrate. Tinting is the process of adjusting the color of completed mill base
dispersions. Various combinations of pigments, solvents, resins, and pastes are added to the
material to meet the color requirements. Blending is the process of incorporating the additions
into the material in order to meet the desired product specifications.13
The final step in paint and ink manufacturing is product filling operations. After the
material has been blended, it is transferred from the blend tanks into containers for product
shipment. The transfer step normally involves product filtration.13
5.2.2 Emissions
The primary factors affecting the emission of methyl chloroform are the types of solvents
and resins used in the manufacturing process, the temperature at which these compounds are
mixed, and the methods and materials used during cleanup operations.13
Methyl chloroform is released from several types of equipment and handling operations
throughout the paint and ink manufacturing process and during cleanup operations. During the
preassembly and premix stage, equipment such as mix tanks or drums may produce emissions
while resins are being thinned and materials are being added. Methyl chloroform emissions also
occur during the pigment grinding step when materials are added to the dispersion equipment.
The emissions that occur during the product finishing step are mainly a result of material
additions during the thinning and tinting stages. Another emission source is product filtering.
As product flows through a filtering device, it may be exposed to the air, resulting in releases
of the incorporated methyl chloroform. Methyl chloroform emissions during filling operations
result from product free-fall and material splashing. Fugitive emissions also result from flanges,
valves, and pumps used to transfer material from equipment for one manufacturing stage to
equipment for the next stage.13 Emissions occurring during the manufacturing stages may be
reduced by using equipment and process modifications such as tank lids or closed-system milling
equipment.
5-15
-------
In addition to emissions from process operations, methyl chloroform is also released from
a variety of cleaning operations following the manufacture of solvent based products. In many
facilities, manufacturing equipment is cleaned manually (with solvents, brushes, and/or rags) on
the production floor on an as-needed basis. The standard method of cleaning grinding equipment
involves emptying the mill of product and then adding solvent to the vessel to capture remaining
product residue. Emissions occur during cleaning solvent addition and removal, as well as during
the cleaning process.13 Emissions from cleaning equipment may be reduced by using rubber
wipers, high-pressure spray heads, or automatic tub washers.13
There is little emission factor information available for the manufacture of paints and inks.
Figures range from process solvent losses of one to two percent under well controlled conditions
to much higher percentages. The process solvent losses vary significantly from facility to facility
and therefore these emissions should be evaluated on a case by case basis. Many paint and ink
manufacturing facilities calculate total plant VOC emissions based on raw material consumption
rather than calculating emissions from processes or equipment by an alternative method. Total
emissions therefore reflect solvent losses during manufacturing, cleaning operations, and storage.13
5.3 AEROSOL MANUFACTURING
Methyl chloroform is used as a vapor pressure depressant in many aerosol formulations,
particularly in personal care products. Methyl chloroform is also used as a formulating solvent
and carrier in aerosol products such as spray paints, insecticides, and auto care items (e.g.,
lubricants, degreasers, and brake cleaners).2'4 Some of the aerosol products known to contain
methyl chloroform are listed in Table 5-4. In 1987, approximately 36 million kgs (80 million
Ibs) of methyl chloroform were consumed in aerosol formulations. Consumption is expected to
drop to 27 million kgs (60 million Ibs) in 1992.4
It has been estimated that the use of aerosol formulations accounts for releases of
approximately 20 million kgs (44 million Ibs) of methyl chloroform each year. Of this amount,
over 18 million kgs (40 million Ibs) are released to the air. The remaining amount is contained
5-16
-------
TABLE 5-4.
AEROSOL PRODUCTS CONTAINING METHYL
CHLOROFORM
Product Category
Household Products:
Automotive:
Coatings and Finishes:
Registered Pesticides:
End-Use
Adhesives
Dusting spray
Leather and suede products
shoe polish formulation
suede cleaner and conditioner
Spot remover
Fabric protector/water repellant
Metal cleaner/protective polish
Exhaust fan and hood cleaner
Mattress refresher
T^L-CI ,, /,--.,, -.-.-.--,!
a,tinjii/itnt w ai * *
Engine degreaser and cleaner
Brake cleaner
Belt dressings
Lubricants
Lacquer stains
Fixative and protective coatings
Racing bottom treatment reagent
Polvurethane coatings
Dog Shield - Dog Repellant
Prentox - 50% DDVP cone.
Prentox - DDVP - aerosol cone.
#G-1533
Prentox DDVP aerosol cone.
Capitol DDVP cone, aerosol
Fumo - aero-spray
Bruce Terminex
Clipper Mate
Stephenson Chem. - DDVAP 14°/
Stephenson Chem. - DD-VP-20%
Carmel Chem. - nonflammable
vapona fogging insecticide
Carmel Chem. - nonflammable
tobacco - pyrethrum spray
form F-13
Pybutox - aerosol - F-201 D
Gabriel DD-VP-90% cone.
Moorehead 5% DD-VP spray
Moorehead 10% DD-VP spray
Moorehead 50% - WE cone.
Swit - wasp and hornet spray
Anti Shield
Comments
Personal protection from dog
For manufacturing purposes only
Industrial use only
Professional insecticide
Lubricates, sanitizers cools
I
Insecticide
Tobacco insecticide
Insecticide/miticide
Insecticide/miticide
Tobacco warehouses
Tobacco warehouses
Insecticide
Source: Reference 15.
5-17
-------
in solid waste. These figures are based on the assumption that 90 percent of an aerosol
formulation is sprayed. An additional 5 percent is lost to the air due to container breakage prior
to or during disposal. The remaining 5 percent remains in the packaging container and is sent
to landfills.15
5.4 ADHESIVE MANUFACTURING
Adhesives are substances used to bond two or more materials by surface attachment.
They are generally applied to facilitate the bonding of paper, wood, ceramics, cork, and other
materials. The three basic types of adhesives are structural adhesives, holding adhesives, and
caulking or sealing adhesives. Structural adhesives are used when the bond is required to be as
strong, if not stronger, than the materials of the parts. Holding adhesives are used to keep
materials in their position, as tiles on a floor or wall. Adhesives used to fill in cracks and voids
are caulking or sealing adhesives.16 Adhesives may also be either organic, inorganic, or hybrids
and consist of either water or solvent carriers.17 Methyl chloroform is often used as a solvent
raw material in the manufacture of synthetic, organic, solvent-based, holding adhesives. Solvent-
based adhesive formulations contain approximately 67 percent by weight solvent and 33 percent
by weight coating solids. The coating solids portion of the formulation consists of elastomers
(e.g., natural rubber, styrene-butadiene rubber, polyacrylates), tackifying resins (e.g., polyterpene
resins, petroleum hydrocarbon resins, and asphalts), plasticizers (e.g., phthalate esters,
polybutenes, mineral oil), and fillers (zinc oxide, silica, clay). Some of the commonly used
adhesive solvents include toluene, xylene, heptane, hexane, methyl ethyl ketone (MEK), and
1 8
acetates.
Methyl chloroform is frequently a substitute for ethyl acetate or methyl ethyl ketone in
urethane adhesives used to laminate flexible packaging films.4'17 In 1987, 29 million kgs (65
million Ibs) of methyl chloroform were consumed in adhesives. Methyl chloroform consumption
is expected to remain constant through 1992.4 This consumption accounts for approximately 10
percent of methyl chloroform end-uses.23 Table 5-5 lists adhesive subcategories and the number
of facilities within these subcategories using methyl chloroform-based formulations.
5-18
-------
TABLE 5-5.
ADHESIVE SUBCATEGORIES AND NUMBER OF
CHLOROFORM
FACILITIES USING METHYL
Adhesive
Sub category
Solution of protein material in water
Solution of carbohydrates in water
Solution of inorganic materials in water
Dispersion of natural elastomer in water
Solutions or dispersions of other natural organics
in water
Solutions or dispersions of synthetic elastomers
in water
Solutions, emulsions, dispersions of synthetic
resins in water
Solutions of natural organic compound in water
Solutions, dispersions of natural elastomer in
solvent
Solutions of synthetic resin in solvent
Solution of synthetic elastomer in solvent
100% synthetic or natural resin, "hot melt"
products
Chemically reactive
Dry blends
Others
Number of Plants
Manufacturing
Sub category
87
110
31
74
46
113
208
54
48
139
116
79
73
45
14
Annual Production in
million kgs
(million Ibs)
90.3 (199)
129.4 (285.2)
518 (1,141.7)
15 (33.1)
23 (50.7)
532 (1,172.5)
606.6 (1,336.9)
44.5 (98.1)
29.5 (65.0)
91.3 (201.2)
164 (361.4)
180.1 (396.9)
52.7 (116.2)
78.5 (173)
33.2 (73.2)
Percent of Plants
Using Methyl
Chloroform in
Sub category
Adhesive
Formulation
0
7
3
3
9
6
23
9
17
15
34
0
1
0
43
Source: Reference 15.
-------
Emissions of methyl chloroform are expected to result from both the manufacturing and
application of methyl chloroform-containing adhesives. Emission sources from the manufacture
of adhesives are expected to be similar to those encountered in the manufacture of paints and
inks as the manufacturing processes are similar. A discussion of these emissions is included in
Section 5.2.2; however, specific emission factors for methyl chloroform adhesive manufacturing
were unavailable at the time this document was prepared.
Emissions resulting from the coating or application of methyl chloroform-containing
adhesives occur primarily at the point of application and in the drying area/oven. In an
uncontrolled facility, essentially 100 percent of the solvent used in the adhesive formulation is
emitted to the atmosphere. Additional losses occur from solvent storage and handling, equipment
cleaning, and miscellaneous spills.19 Controls used in the application of adhesives are similar to
those used in the application of other surface coatings. A general discussion of these controls
is included in Section 6.1. Total methyl chloroform emissions from the use of adhesive
formulations have been estimated to be 19.8 million kgs (43.6 million Ibs). Of this quantity, 17.4
million kgs (38.3 million Ibs) are emitted to the air, 0.9 million kgs (2.0 million Ibs) are released
as solid waste, 0.3 million kgs (0.7 million Ibs) are released to water, 57 thousand kgs (125
thousand Ibs) are destroyed, and 1 million kgs (2.2 million Ibs) are recovered.15
5.5 CHEMICAL INTERMEDIATES
Chlorofluorocarbons (CFCs) are compounds composed of carbon, fluorine, chlorine and
hydrogen and are used chiefly as refrigerants. CFCs are also used in air-conditioning equipment,
as blowing agents, fire extinguishing agents, and cleaning fluids and solvents. They are
sometimes erroneously referred to as fireons which is actually a Trademark name for a series of
CFC products. HCFCs are compounds comprised of carbon, fluorine, chlorine, and an additional
halogen, usually bromine and have been developed as substitutes for some CFC applications.
The term halon is also a Trademark name for a series of fluorinated brominated CFCs.
5-20
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Methyl chloroform is used as a chemical intermediate in the synthesis of several HCFCs
including HCFC-142b and HCFC-141b, and several halons such as halon-1211
®
(bromochlorodifluoromethane), halon-1301 orFreon 13B1 (bromotrifluoromethane), andhalon-
2402 (dibromotetrafluoroethane). Neither HCFC-141b nor HCFC-142b is subject to the Montreal
Protocol requirements for the year 2000, or 1990 CAAA consumption and production phase-outs
as discussed in Section 3.2; however, both are 1990 CAAA Class II substances which are
scheduled for phase-out by 2020.4'20
HCFC-142b, manufactured by Pennwalt Corporation in Calvert City, Kentucky and
Thorofare, New Jersey, is a precursor for the vinylidene fluoride monomer introduced in 1984
as a propellant for premium fragrances. Pennwalt is also selling mixtures of HCFC-142b and
HCFC-22 having properties similar to those of chlorofluorocarbon (CFC)-ll and CFC-12. In
addition, Pennwalt is evaluating HCFC-141b, a co-product in the manufacture of HCFC-142b,
as an alternative to CFC-11 used as a blowing agent in the manufacture of flexible and rigid
polyurethane foams and polystyrene and polyethylene foams. In spite of their advantages as
potential CFC replacements, HCFC-142b and HCFC-141b are more expensive than CFC-11 and
CFC-12, and they are moderately flammable. In 1987, nearly 18 million kgs (40 million Ibs) of
methyl chloroform were consumed in the manufacture of HCFC-142b.4
Although production of the three halons (i.e.., halon-1211, halon-1301, and halon-2402)
is restricted by both the Montreal Protocol and the 1990 CAAA and they are scheduled for phase-
out by the year 2000, small quantities may continue to be produced after the year 2000. All
three of these chemicals are used in nondestructive testing for metal fatigue and corrosion of
existing airplane engines and airplane parts susceptible to metal fatigue and may qualify for the
aviation safety exemption of the 1990 CAAA. The Federal Aviation Administration must provide
a report to Congress in 1998 which addresses the use of these halons, and other chemicals
scheduled for phase-out, in aviation safety.20
Methyl chloroform emissions from the manufacture and use of halons, CFCs, and HCFCs
were unavailable at the time this document was prepared.
5-21
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5.6 MISCELLANEOUS END USES OF METHYL CHLOROFORM
Methyl chloroform is used in several applications in textile processing including scouring
agents, equipment cleaning, dye carriers, and spotting fluids. Equipment cleaning may be
accomplished by one of the methods discussed in Section 5.1 or by wipe cleaning, a process in
which equipment (primarily texturizing machines) is merely wiped down with a solvent-laden
cloth.4'15 Dye carriers transfer the pigment particles from the dye solution to the fiber while
scouring agents remove the natural (e.g., waxes, oils, and pectins) and applied (e.g., identification
paints, insecticides, or bactericides) impurities from natural fibers such as cotton and wool.21
These uses accounted for 5.4 million kgs (12 million Ibs) of methyl chloroform consumption in
1989 2-4 T^ 1992 consumption of methyl chloroform in textile applications is expected to be
nearly 7 million kilograms (15 million pounds).4
Methyl chloroform has several uses within the electronics industry. Methyl chloroform
is the preferred solvent for the cleaning of printed circuit boards, as was mentioned in
Section 5.1. It is used to remove the flux left on the boards after the soldering of surface
mounted devices. Methyl chloroform is also used as a developer of dry film photoresists in the
solvent processing of printed circuit boards. This use, however, is expected to decrease with the
increased use of aqueous cleaners. Another end use of methyl chloroform in the electronics
industry is the in situ production of plasma etchant gases used in the production of
semiconductors. Total methyl chloroform consumption in the electronics industry was 11 million
kgs (25 million Ibs) in 1987. Electronic industry consumption is anticipated to decline to
9 million kgs (20 million Ibs) in 1992.4
Additional end uses of methyl chloroform include use as a coolant and lubricant in cutting
oils, a component in plastic film (e.g., movie, video, television film) cleaners, and a carrier
solvent for silicone paper coatings and protective coatings. The total methyl chloroform
consumption in miscellaneous uses was 21 million kgs (46 million Ibs) in 1987. Miscellaneous
use consumption is anticipated to decline to 20 million kgs (45 million Ibs) in 1992.4
5-22
-------
No emissions data are available for textile processing, electronics manufacturing, or other
miscellaneous uses of methyl chloroform. To determine actual emissions from particular
processes, specific plants should be contacted.
5-23
-------
5.7 REFERENCES FOR SECTION 5.0
1. Considine, Douglas M., ed., Chemical and Process Technology Encyclopedia. McGraw-
Hill Book Company, New York, NY. 1974.
2. "1,1,1-Trichloroethane," Chemical Products Synopsis. Mannsville Chemical Products,
Asbury Park, NJ. October 1990.
3. "Chemical Profile: 1,1,1-Trichloroethane," Chemical Marketing Reporter. January 27,
1992.
4. "C2 Chlorinated Solvents," Chemical and Economics Handbook, SRI International, Menlo
Park, CA. December 1988.
5. U.S. Environmental Protection Agency. Alternative Control Technology Document -
Halogenated Solvent Cleaners. EPA-450/3-89-030. Office of Air Quality Planning and
Standards. Research Triangle Park, NC. August 1989.
6. Toxic Chemical Release Inventory (TRI). 1990.
7. Archer, W.L., "Other Chloroethanes," Kirk-Othmer Encyclopedia of Chemical Technology,
Third Edition, Vol. 5. 1979. pp. 722-742. 1979.
8. U.S. Environmental Protection Agency. Locating and Estimating Air Emissions from
Sources of Perchloroethylene and Trichloroethylene. EPA-450/2-89-013. Office of Air
Quality Planning and Standards. Research Triangle Park, NC. August 1989.
9. U.S. Environmental Protection Agency. Control of Volatile Organic Emissions from
Solvent Metal Cleaning. EPA-450/2-77-022. Office of Air Quality Planning and
Standards. Research Triangle Park, NC. November 1977.
10. U.S. Environmental Protection Agency. Organic Solvent Cleaners - Background
Information on Proposed Standards. EPA-450/2-78-045a. Office of Air Quality Planning
and Standards. Research Triangle Park, NC. October 1979.
11. Sheiman, Deborah, et a/., A Who's Who of American Ozone Depleters: A Guide to
3,014 Factories Emitting Three Ozone Depleting Chemicals. Natural Resources Defense
Council. January 1990.
12. SRI International. U.S. Paint Industry Database. Prepared for the National Paint and
Coatings Association. Washington, DC. 1990.
13. U.S. Environmental Protection Agency. Control of VOC Emissions from Ink and Paint
Manufacturing Processes. EPA-450/3-92-013. Office of Air Quality Planning and
Standards. Research Triangle Park, NC. 1991.
5-24
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14. Gale Research, Inc. Ward's Business Directory of U.S. Private and Public Companies-
1991, Volume 4. Detroit, MI. 1991.
15. Memorandum from Michael A. Callahan, U.S. Environmental Protection Agency, TSPC
Solvents Work Group #2, to Elizabeth Anderson, U.S. Environmental Protection Agency,
TSPC Solvents Work Group #1, "Draft Exposure Assessment for TSPC Solvents." Public
Docket No. A-84-41, II-B-1.
16. Considine, Douglas M., ed., Chemical and Process Technology Encyclopedia. McGraw-
Hill, Inc. pp. 38-39. 1974.
17. U.S. Environmental Protection Agency. Summary of Technical Information for Selected
Volatile Organic Compound Source Categories. EPA-450/3-81-007. Office of Air
Quality Planning and Standards. Research Triangle Park, NC. May 1981.
18. U.S. Environmental Protection Agency. Compilation of Air Pollutant Emission Factors.
AP-42, Fourth Edition and Supplements, Office of Air Quality Planning and Standards.
Research Triangle Park, NC. pp. 4.2.2.9-1 and 4.2.2.9-3. 1985.
19. U.S. Environmental Protection Agency. Procedures for the Preparation of Emission
Inventories for Carbon Monoxide and Precursors of Ozone - Volume /EPA-450/4-91-016.
Office of Air Quality Planning and Standards. Research Triangle Park, NC. May 1991.
20. Public Law 101-549. The Clean Air Act Amendments of 1990, Title VI - Stratospheric
Ozone Protection. November 15, 1990.
21. U.S. Environmental Protection Agency. Control Techniques for Volatile Organic
Emissions from Stationary Sources. EPA-450/2-78-022. Office of Air Quality Planning
and Standards. Research Triangle Park, NC. May 1978.
5-25
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SECTION 6.0
RESIDUAL AND BY-PRODUCT EMISSIONS OF METHYL CHLOROFORM
This section examines residual emissions from the use or processing of methyl
chloroform-containing materials. Methyl chloroform may be emitted when methyl chloroform-
containing products such as paint and coatings release small amounts over time. Methyl
chloroform emissions can also occur as the result of the manufacture of another product. These
emissions are described in this section as by-product emissions. Pulp processing is a process
leading to by-product emissions of methyl chloroform.
The production descriptions and emissions data presented in this section represent some
of the most common and relevant processes and products. Because of methyl chloroform's
widespread use, all processes cannot be included in this document.
6.1 SURFACE COATING OPERATIONS
Surface coating operations involve the application of paint, varnish, lacquer or primer for
decorative, functional, or protective purposes. In 1989, 10.2 million kgs (22.5 million Ibs) of
methyl chloroform were consumed in paints and coatings.1 Consumption of solvents in specific
end-use markets was presented in Section 5.2, Table 5-3. Table 6-1 contains a list of surface
coating source categories and associated SICs in which methyl chloroform is used. Table 6-1
also presents potential methyl chloroform emission points and emissions reduction opportunities.
References are provided for additional information.
The general application methods for surface coating operations are discussed below.
Because surface coating is a very broad category, detailed process descriptions and process flow
diagrams for each category are not included in this document; however, the reader is encouraged
to review the references mentioned at the end of this section and in Table 6-1.
6-1
-------
TABLE 6-1.
METHYL CHLOROFORM SOURCE CATEGORIES IN
SURFACE COATING OPERATIONS
General Source Category
Associated SIC(s)
Emission Point Sources
Emissions reduction by Additional
process/product modification References
Paper and Paperboard
2621, 2631, 2652-
53, 2656, 2657,
2671-72, 2675,
2676, 2678-79
[1] Application area
[2] Oven areas
[3] Coating mixing
[4] Coating and solvent storage
[5] Equipment cleanup
[6] All solvent used and not recovered or destroyed
can be considered potential emission sources
[1] Carbon adsorber
[2] Thermal incinerator
[3] Catalytic incinerator
[4] Condensers
Adhesives and Sealants
2891
[1] Adhesive application
[2] Drying oven exhaust
[3] Solvent mixing
[4] Solvent storage
[5] All solvent used and not recovered or destroyed
can be considered potential emission sources
[1] Thermal incineration
[2] Carbon adsorption
9,10
to
Wood Products
2426-29, 2434,
452,2511-12,
2515,2517,2519,
2521,2531,2541,
3995
[1] Application area
[2] Flashoff coating operations
[3] Oven areas
[4] Coating mixing
[5] Coating and solvent storage
[6] Equipment cleanup
[7] All solvent used and not recovered or destroyed
can be considered potential emission sources
[1] Waterborne coatings
[2] Carbon adsorption
[3] Thermal incineration
[4] Catalytic incineration
11
Flatwood Products
2435-36, 2491-99
[1] Application area
[2] Flashoff area:
Filler, sealer, basecoat, topcoat, inks
[3] Oven areas
[4] Coating mixing
[5] Coating and solvent storage
[6] Equipment cleanup
[7] All solvent used and not recovered or destroyed
can be considered potential emission sources
[1] Waterborne coating for filler
and basecoat
[2] Ultraviolet cure coatings
[3] Afterburners
[4] Carbon adsorption
12,13
Source: References 2-7.
-------
6.1.1 Process Description
Industrial surface coating operations use several different methods to apply coatings to
substrates. Some of the more commonly used techniques include spraying, dipping, rolling, flow
coating, knife coating, and brushing. In addition to the application of coatings to substrates,
many surface coating operations also include surface preparation steps (e.g., cleaning and
degreasing), drying and curing stages. Spraying operations are normally performed in a spray
booth using one of the following spray application methods: air atomization; airless atomization;
air-assisted airless; high-volume, low-pressure (HVLP); and electrostatic. Dip coating involves
briefly immersing the substrate in a tank containing a bath of paint. The object is slowly
removed from the tank, allowing excess paint to drain back into the tank. Roller coating is used
to apply coatings and inks to flat surfaces. A typical roller coating machine contains three or
more power driven rollers, one of which is partially immersed in the coating material. The paint
is transferred to a second, parallel roller by direct contact. The sheet to be coated is run between
the second and third rollers, and is coated by transfer of paint from the second roller. Flow
coating is used on articles which cannot be dipped due to their buoyancy, such as fuel oil tanks,
gas cylinders, or pressure bottles. In this operation the coating material is fed through overhead
nozzles which apply the paint in a steady stream over the article to be coated. Excess paint is
allowed to drain from the coated object and is then recycled. Knife coating is used primarily to
coat paper or fabric webs. The adjustable blade or "knife" distributes a liquid coating evenly
over a moving surface.
6.1.2 Emissions14-15
Figure 6-1 is a generic flow diagram of a surface coating operation. Process operations,
auxiliary facilities, and emission points are illustrated. Note that this is a generic figure and may
differ significantly from any specific coating operation. The operations shown include
degreasing, surface coating, and drying and curing. Auxiliary facilities include degreasing solvent
storage, surface coating storage and blending, and steam generation. Industrial categories,
6-3
-------
o\
DECREASING SOLVENT
STORAGE TANK
SURFACE COATING
BLENDING TANK
SURFACE COATING
SOLVENT STORAGE
TANK
y
Figure 6-1. Flow diagram of a surface coating operation."
-------
specific operations and emission points resulting in expected methyl chloroform emissions from
surface coating operations are presented in Table 6-1 and as part of Appendix A.
Streams 1, 2, 3, and 4 depict the flow of products through the plant. Stream 1 represents
the input of uncoated products to the surface coating system. Stream 2 represents the flow of
degreased or scoured products to the surface coating operation. The type of surface coating
operation used will depend upon the product-type coated, coating requirements, and the method
of application. Stream 3 represents the product flow to the drying and curing operation. Stream
4 represents the flow of coated finished products from the surface coating section of a
manufacturing plant.
Streams 5 through 10 represent the flow of degreasing solvent through the surface coating
section of a manufacturing plant. Streams 5 and 6 depict the flow of solvent into the plant and
to the degreasing unit. Streams 7 and 8 represent the flow of solvent vapors from the degreasing
unit through the fume handling system. Uncontrolled and controlled emissions are represented
by streams 9 and 10, respectively.
Streams 11 through 21 represent the flow of surface coating raw materials through the
plant. Streams 11, 12, 13, and 14 represent the flow of solvent, pigment, resin, and additives to
the surface coating blending tank. Stream 15 is the flow of coating to the surface coating unit.
For those operations that use spray painting, stream 16 is the flow of compressed air. Streams
18 and 19 represent the flow of solvent and resin from the surface coating unit through the fume
handling equipment. Uncontrolled and controlled emissions are depicted by streams 20 and 21.
Potential emission point sources were previously identified in Table 6-1.
In Figure 6-1, streams 22 through 25 represent the flow of gases (e.g., fuel, steam or
electrically heated air) to the drying and curing operation. Drying and curing operations occur
in flash-off areas and curing ovens. Flash-off areas are the places between application areas, or
between an application area and an oven, in which solvent is allowed to volatilize from the
coated piece. Ovens are used between some coating steps to cure the coating prior to the next
6-5
-------
step in the finishing sequence. Streams 24 and 25 represent uncontrolled and controlled
emissions. No emission factor data were found in the literature.
Facilities with surface coating operations may purchase and apply ready-to-use coatings,
or they may dilute their purchased coatings to decrease the coating viscosity and improve
performance and ease of application. Methyl chloroform is used in solvent-based coating
formulations either as part of the coating vehicle or as a thinner. If a coating formulation is to
be diluted in-house, several factors (e.g., temperature, humidity, and type of coating) can
determine the required dilution ratio. Consequently, the amount of methyl chloroform used may
vary.2'14'16'17 Emissions from the mixing and blending of surface coatings were previously
discussed in Section 5.2.2.
Methyl chloroform may also be used in clean-up operations. Clean-up solvent is used to
clean application equipment, piping, spray booths, coating storage and distribution equipment,
and to strip cured coatings from wood parts or machinery.14
One method of reducing methyl chloroform emissions from surface-coating operations is
to modify the surface-coating formulation. Conventional coatings normally contain at least 70
percent by volume solvent (either one solvent or a mixture of solvents) to permit easy handling
and application. Minimizing or eliminating the use of these solvents in surface-coating
formulations is the most effective way to reduce VOC emissions. Alternatives to these
conventional coatings include water-based coatings, high-solids coatings, powder coatings, and
radiation-curable coatings.14
Large surface-coating facilities may use add-on control devices to capture and control
solvent emissions. Some commonly used capture devices include covers, vents, hoods, and
partial or total enclosures. Adsorbers, condensers and incinerators, with control efficiencies of
95 to 98 percent, are the most common control devices used in surface coating operations.14'16'17
6-6
-------
6.2 WASTEWATER TREATMENT PROCESSES
Atmospheric emissions of volatile organic compounds such as methyl chloroform can
occur at any wastewater treatment process where the wastewater comes into contact with the
surrounding ambient air. The majority of air emissions from wastewater treatment facilities may
be expected from the initial physical processes (e.g., screening, sedimentation, floatation, and
filtration), due to both a higher pollutant concentration in the influent and a greater surface area
caused by turbulence and mixing. Other sources of emissions include equalization and aeration
basins, and clarifiers. Significant volatile organic compound emissions may occur if an oil/water
separation treatment step is incorporated within the process. The lighter organic compounds rise
within the wastewater to form an oil-based layer that rests on top of the main body of wastewater
in the separation basin. Factors affecting volatilization of organic compounds from the top
organic layer include characteristics of the wastewater and oil layers, the ambient wind speed,
design characteristics of the wastewater treatment operation, the concentration of pollutants in
the wastewater, detention time in the treatment system, and partition coefficients of the
pollutants.18'19
Methyl chloroform has been estimated as one of the most pervasive volatile organic
compounds emitted from publicly owned treatment works (POTWs) nationally, with
approximately 3 million kgs (6.6 million Ibs) emitted per year prior to 1986.20 A study of two
wastewater treatment facilities in the Chicago area revealed that volatilization is the primary
removal mechanism of methyl chloroform from wastewater. Adsorption and biodegradation
removal mechanisms were insignificant and absent, respectively. Estimated total methyl
chloroform emissions from the two facilities in the Chicago study were 9,299 kgs (20,460 Ibs)
per year.21 A California-based study of uncontrolled statewide municipal wastewater treatment
plants (51 plants in sample) estimated methyl chloroform emissions of 90,900 kgs (200,000 Ibs)
per year.22 Finally, a 1989 volatile organic compound receptor modeling study cites significant
methyl chloroform emissions data from two in-plant ambient air studies and three modeling
studies.23
6-7
-------
Because of the many factors that may affect emissions of volatile organics, including
methyl chloroform, from wastewater treatment processes, estimating actual emissions must be
performed on a chemical-by-chemical, process-by-process basis. Several models have been
developed that estimate emissions from wastewater treatment processes. A brief description of
some appropriate models are presented below; however, further information should be consulted
in the appropriate reference(s) provided in Section 6.4.24"28
The SIMS model (Surface Impoundment Modeling System), developed by the Control
Technology Center of the U.S. Environmental Protection Agency, is a personal computer-based
software program designed to estimate atmospheric emissions from surface impoundments and
wastewater collection devices.24 Emissions estimates are based on mass transfer models
developed by the Emissions Standards Division (ESD) of the EPA and are available for 147
compounds.
CHEMDAT7 is a spreadsheet program developed by the Office of Air Quality Planning
and Standards, EPA, that includes analytical models for estimating volatile organic compound
emissions from hazardous waste, treatment, storage, and disposal facility (TSDF) processes under
user-specified input parameters.25 This model only addresses emissions through volatilization and
biodegradation mechanisms, and includes emissions from non-aerated, aerated, and disposal
impoundments, land treatment, and landfills. The CHEMDAT7 database covers 700 compounds.
The Civil Engineering Department at the University of California, Davis, along with
CH2M-Hill and the Bay Area Air Toxics Group, developed the Bay Area Sewage Toxics
Emission (BASTE) Model that can estimate VOC losses from a series of wastewater treatment
processes for an entire treatment facility.26 The BASTE Model can calculate losses associated
with volatilization, adsorption, and biodegradation of VOCs, and it does allow for temperature
changes and will model all aspects of a POTW. This model can simulate completely mixed
systems, but is limited to the number of chemicals it will allow to be input into the model. The
input parameters are generally more complex than for the other models, yet the BASTE model
provides a higher degree of flexibility.26
6-8
-------
Another model for estimating VOCs from wastewater treatment facilities was developed
by Camp Dresser & McKee of Boston, MA, for estimating VOC emissions for a future plant.27
According to the Pincince model, approximately 95 percent of the total VOC emissions occur at
weirs such as the primary and secondary splitter boxes, at the grit chamber and primary clarifier
weirs, and at the ends of the aeration tanks. Approximately four percent of the total VOC
emissions were from the aeration tanks when high-purity oxygen was used. These estimates are
considered conservative, since the Pincince model does not account for compounds which are
adsorbed and subsequently released. Factors that the model does consider include Henry's law
coefficients, the octonal-water partition coefficient (Kow), the nature of the air/water interface,
wind speed, and process design parameters.
The Tsivoglou and Neal Reaeration model can be used with the SIMS model to estimate
VOC emissions from the devices that comprise the headworks of a POTW (since the SIMS
model does not account for emissions from these devices or for adsorption onto solids).28 This
Reaeration model estimates the oxygen mass transfer rate constant as a function of the change
in elevation and time of flow between two locations in a stream. The oxygen mass transfer
coefficient is then adjusted to estimate the VOC mass transfer coefficient.
Several inherent problems exist with using these models. First, the VOC concentrations
in the wastewater are highly variable among the influent, effluent, and sludge partitions;
therefore, a single emission estimate would be highly questionable. Second, the estimates are
usually based on constant behavior of relatively pure compounds, so mixing and variable
chemical concentrations would render the emission factors less useful. Finally, these estimates
are generally on the conservative side, and actual emissions will often tend to be higher than the
estimates.
6-9
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6.3 PULP AND PAPER PRODUCTION
6.3.1 Description of Pulp Processing
Pulping consists of converting raw materials into fibers which can be used in products
such as paper, paperboard, or building materials. Although the raw materials include fibers from
waste paper (i.e., secondary fibers), cotton or wool, the principle source is wood fibers from trees
(i.e.., virgin fibers). Wood pulp is treated either mechanically or chemically to liberate the fibers.
Chemical processes [including kraft (sulfate), sulfite, neutral sulfite semichemical (NSSC), or
soda pulping] produce fibers by dissolving the binding material in the wood (i.e., the lignin) in
chemical solutions.29
Kraft (sulfate) pulping is the most common pulping method in the United States. In 1990,
paper and paperboard mills consumed 55 million kgs (122 million Ibs) of wood pulp. Bleached
sulfate accounted for 24 million kgs (52 million Ibs) and unbleached sulfate accounted for 20
million kgs (45 million Ibs).30 An overview of the kraft pulping process is presented in
Figure 6-2. Wood chips are normally loaded into a batch digester where they are cooked at
elevated temperatures of 170° to 180°C (338° to 356°F) and pressure in a "white liquor." The
white liquor is typically a water solution of sodium sulfide and sodium hydroxide.3132 Once the
liquor has dissolved the lignin and loosened the wood fibers, the wood chip mixture is transferred
to a blow tank where the fibers are freed. The mixture then moves to a pulp filter which
separates the pulp from knots, chips, uncooked pieces of wood, and the cooking liquor. The
wood pulp proceeds through various stages of washing, and often bleaching, after which it is
pressed and dried into the final product.29'32
Bleaching is often included as part of the pulp treating process to improve the intensity
and permanency of the whiteness in the pulp. Bleaching uses chlorine and chlorine compounds
in three different forms. In the chlorination stage, pulp is treated with gaseous chlorine primarily
to oxidize and chlorinate the remaining lignin which is then dissolved from the pulp in successive
steps. The pulp is washed and sent to the caustic extraction stage where sodium hydroxide
6-10
-------
H2S. CHjSH. CHjSCH3
and Higher Compounds
Chips
CHjSH, CH3SCHj. H2S
Noncondensables
CH3SH, CHjSCHj, H2S
Noncondensables
Turpentine
Contaminated Water
Steam. Contaminated Water,
H2S. and CH3SH
Pulp
Spont Air, CHjSCHjT1
and CHjSSCHj
n
1 ,
<
Evaporator
1
Black Liquor
SOX Solids
Na2S
NaOH
TCA
Emissions
Bleaching
Direct Contact
Evaporator
[ Black
70% Solids _.
2S04
(
1 "I
IWater
Recovery
Furnace
Oxidizing
Zone
Reduction
Zone
Sulfur
Smelt |
Ka2S+Na2CO3
Pulp Washing
Air
Waste Water
(may contain TCA)
Figure 6-2. Typical kraft sulfate pulping and recovery process."
-------
(pH 12) breaks down and removes the lignin. A second washing occurs after which the pulp is
treated with sodium hypochlorite and/or peroxide.32'33
The remainder of the kraft process is designed t3 recover the heat and cooking chemicals
from the digester. The spent cooking liquor and the pulp wash water are combined to form a
weak black liquor which is concentrated to 55 percent solids in a multiple-effect evaporator and
then further concentrated to 65 percent solids in a direct-contact evaporator using flue gases from
the recovery furnace. The concentrated black liquor is fired in a recovery furnace where organics
in the liquor are burned to provide heat for steam. The inorganic portion of the black liquor
collects as molten smelt at the bottom of the furnace. The smelt is dissolved in water to form
green liquor and then transferred to a causticizing tank where quicklime (calcium oxide) is added
to convert the solution back to white liquor for return to the digester system.32
6.3.2 Atmospheric Emissions from Pulp Processing
The primary emissions from pulping operations are reduced sulfur compounds such as
hydrogen sulfide, methylmercaptan, dimethyl sulfide, and dimethyl disulfide.32 However, the
Toxic Chemical Release Inventory (TRI) indicates that facilities classified under SIC 2611 (Pulp
Mills) emit significant amounts of methyl chloroform. Upon contacting TRI facilities classified
under SIC 2611, it was discovered that the majority of atmospheric emissions of methyl
chloroform occur from secondary processes such as paper coating or equipment cleaning. One
facility did report that both air and water emissions of methyl chloroform resulted from reactions
occurring during the bleaching process.34 This facility also cited the Handbook of Chemical
Specific Information for SARA 313 Form R Reporting, a publication distributed by the National
Council of the Paper Industry for Air and Stream Improvement, as documenting these emissions
and describing the environmental fate of methyl chloroform.35 This document was unavailable
for use in preparing this report.
6-12
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6.4 REFERENCES FOR SECTION 6.0
1. SRI International. U.S. Paint Industry Database. Prepared for the National Paint and
Coatings Association. Washington, DC. 1990.
2. U.S. Environmental Protection Agency. VOC Pollution Prevention Options for the
Surface Coating Industry. Research Triangle Park, NC. 1991.
3. U.S. Environmental Protection Agency. Procedures from the Preparation of Emission
Inventories for Carbon Monoxide and Precursors of Ozone, Volume I.
EPA-450/4-91-016. Research Triangle Park, NC. May 1991.
4. U.S. Environmental Protection Agency. Recordkeeping Guidance Document for Surface
Coating Operations and the Graphic Arts Industry. EPA-340/1-88-003. Stationary Source
Compliance Division. Washington, DC. December 1988.
5. Ron Joseph and Associates, Inc. Environmental and Coatings Training Program.
Workbook for presentation by Ron Joseph to EPA Region 1. September 2 and 3, 1987.
6. The Bureau of National Affairs, Air Pollution Control. BNA Policy and Practice Series.
Washington, DC.
7. Strait, R. et al. VOC Control Policy in the United States: An Overview of Programs and
Regulations. Alliance Technologies Corporation. Chapel Hill, NC. December 1991.
8. U.S. Environmental Protection Agency. Control of Volatile Organic Emissions from
Existing Stationary Sources. Volume 11: Surface Coating of Cans, Coils, Paper, Fabrics,
Automobiles and Light-Duty Trucks. EPA-450/2-77-088. Research Triangle Park, NC.
1977.
9. U.S. Environmental Protection Agency. Pressure Sensitive Tape and Label Surface
Coating Industry - Background Information for Proposed Standards.
EPA-450/3-80-003A. Research Triangle Park, NC. 1980.
10. U.S. Environmental Protection Agency. Final Environmental Impact Statement Pressure
Sensitive Tape and Label Surface Coating Industry - Background Information for
Promulgated Standards. EPA-450/3-80-003B. Research Triangle Park, NC. 1983.
11. U.S. Environmental Protection Agency. Control of Volatile Organic Compound
Emissions from Wood Furniture Coating Operations. Draft CTG. Research Triangle
Park, NC. October 1991.
12. U.S. Environmental Protection Agency. Enforceability Aspects of RACT for Factory
Surface Coating of Flat Wood Paneling. EPA-340/1-80-005. Washington, DC. 1980.
6-13
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13. U.S. Environmental Protection Agency. Control of Volatile Organic Emissions from
Existing Stationary Sources. Volume 11: Surface Coating of Flatwood Paneling.
EPA-450/2-78-032. Research Triangle Park, NC. 1978.
14. U.S. Environmental Protection Agency. Compilation of Air Pollutant Emission Factors.
AP-42, Fourth Edition and Supplements. Research Triangle Park, NC. 1985.
15. U. S. Environmental Protection Agency. Source Assessment: Prioritization of Air Pollution
from Industrial Surface Operations. EPA-650/2-75-019a. Research Triangle Park, NC.
1975.
16. Bridgewater, A.V. and CJ. Mumford. Water Recycling and Pollution Control Handbook.
Van Nostrand Reinhold Company. 1979.
17. Godish, Thad. Air Quality. Director of the Indoor Air Quality Research Laboratory.
1985.
18. U.S. Environmental Protection Agency. Guideline Series: Control of Volatile Organic
Compound Emissions from Industrial Wastewater, Vol. 1. Preliminary Draft. Office of
Air Quality Planning and Standards. Research Triangle Park, NC. April 1989.
19. U.S. Environmental Protection Agency. VOC Emissions From Petroleum Refinery
Wastewater Systems - Background Information for Proposed Standards. Draft EIS.
EPA-450/3-85-001a. Office of Air Quality Planning and Standards. Research Triangle
Park, NC. February 1985.
20. U.S. Environmental Protection Agency. Report to Congress on the Discharge of
Hazardous Wastes to Publicly Owned Treatment Works. EPA/530-SW-86-004. February
1986.
21. Rittman, Bruce E. and Namkung, Eun. "Estimating Volatile Organic Compound
Emissions from Publicly Owned Treatment Works," Journal of The Water Pollution
Control Federation 59(7):670-678. July 1987.
22. Corsi, Richard L., et al. "Emissions of Volatile and Potentially Toxic Organic Compounds
from Municipal Wastewater Treatment Plants," Presented at the 80th Annual Meeting of
APCA, New York, NY. June 21-26, 1987.
23. Schelf, Peter A., et al. "Source Fingerprints for Receptor Modeling of Volatile Organics,"
Journal of the Air and Waste Management Association (JAPCA) 39(4):469-478. April
1989.
6-14
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24. U.S. Environmental Protection Agency. Surface Impoundment Modeling System (SIMS)
Version 2.0 User's Manual. Control Technology Center. EPA-450/4-90-019a. Research
Triangle Park, NC. 1990.
25. U.S. Environmental Protection Agency. Hazardous Waste Treatment, Storage, and
Disposal Facilities (TSDF) - Air Emissions Models. Review Draft. Office of Air Quality
Planning and Standards. November 1990.
26. BASTE (Bay Area Sewage Toxics Emissions) User's Guide. CH2M-Hill. Document No.
SF0176/060A.51. May 1990.
27. Pincince, A.B. "Calculating Emissions of Volatile Organic Compounds from Wastewater
Treatment Plants," Proceedings of the Winter 1988 Meeting of the New England Water
Pollution Control Association. Boston, MA. 1988.
28. Tsivoglou, E.G., and L.A. Neal. "Tracer Measurement of Reaeration, III, Predicting the
Reaeration Capacity of Inland Streams," Journal of Water Pollution Control Federation
48(12):2669. 1976.
29. Kline, James E., Paper and Paperboard Manufacturing and Converting Fundamentals.
Miller Freeman Publications, Inc. San Francisco, CA. pp. 29-70. 1982.
30. Consumption of Pulpwood, Wood Pulp and Other Fibrous Materials in Paper and
Paperboard Mills. American Paper Institute. Table XXII transmitted via fax on May 29,
1992.
31. Smook, G.S., and MJ. Kocurek, ed. Handbook for Pulp & Paper Technologies. Joint
Textbook Committee of the Paper Industry, Canada, pp. 38-39, 364-367. 1982.
32. U.S. Environmental Protection Agency. "Chemical Wood Pulping," Compilation of Air
Pollutant Emission Factors. AP-42. Fourth Edition and Supplements, Section 10.1,
Research Triangle Park, NC. 1985.
33. Environmental Protection Service, Environment Canada. State-of-the-Art of the Pulp and
Paper Industry and its Environmental Protection Practices. Report EPS 3-EP-84-2.
Environmental Protection Programs Directorate, pp. 60-66. 1984.
34. Personnel communication with R. Sherwood, Pope and Talbot Pulp, Inc., Halsey, Oregon,
by B. McMinn, TRC Environmental Corporation. "TRI Emissions of Methyl
Chloroform." June 22, 1992.
35. National Council of the Paper Industry for Air and Stream Improvement. Handbook of
Chemical Specific Information for SARA 313 Form R Reporting. New York, NY.
6-15
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6-16
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SECTION 7.0
AMBIENT AIR AND STATIONARY SOURCE TEST PROCEDURES
Methyl chloroform (1,1,1-trichloroethane) emissions can be measured from ambient air
and stationary sources utilizing the test methods presented below. If applied to stack sampling,
the ambient air monitoring methods may require adaptation or modification. Appropriate
precautions must be taken to ensure that the capacity of the methodology is not exceeded so that
results will be quantitative. Ambient methods which require the use of sorbents are susceptible
to sorbent saturation if high concentration levels exist. If this happens, breakthrough will occur,
and quantitative analysis will not be possible.
• EPA Method TO-1: Determination of Volatile Organic Compounds in Ambient Air Using
Tenax® Adsorption and Gas Chromatography/Mass Spectrometry (GC/MS)
• EPA Method TO-2: Determination of Volatile Organic Compounds in Ambient Air by
Carbon Molecular Sieve Adsorption and Gas Chromatography/Mass Spectrometry
(GC/MS)
• EPA Method TO-14: Determination of Volatile Organic Compounds (VOCs) in Ambient
Air Using SUMMA® Passivated Canister Sampling and Gas Chromatographic (GC)
Analysis
EPA Method 0030: Volatile Organic Sampling Train (VOST) with EPA Method 5040:
Analysis of Sorbent Cartridges from VOST
The following subsections briefly describe the recommended sampling and analytical methods
for determining methyl chloroform emissions.
7.1 EPA METHOD TO-11
Ambient air concentrations of methyl chloroform can be measured using EPA Method
TO-1 from the Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Air. This method is used to collect and determine volatile nonpolar organics (aromatic
hydrocarbons, chlorinated hydrocarbons) that can be captured on Tenax® and determined by
thermal desorption techniques. The compounds determined by this method have boiling points
7-1
-------
in the range of 80° to 200°C (180° to 390°F). Figure 7-1 presents a schematic of the sampling
system and Figure 7-2 presents a schematic of typical Tenax® cartridge designs.
Ambient air is drawn through the cartridge which contains approximately 1 to 2 grams
(0.035 to 0.07 ounces) of Tenax®. Methyl chloroform is trapped on the Tenax® cartridge which
is then capped and sent to the laboratory for analysis utilizing purge-and-trap gas
chromatography/mass spectrometry (GC/MS) according to the procedures specified in EPA
Method 5040 (see Section 7.5). The recommended GC column is a 50 meter capillary, type SE-
30 with an internal diameter of 0.3 mm.
The exact run time, flow rate and volume sampled varies from source to source depending
on the expected concentrations and the required detection limit. Typically, 10 to 20 L (0.3 to
0.7 ft3) of ambient air are sampled. Analysis should be conducted within 14 days of sample
collection.
7.2 EPA METHOD TO-21
Ambient air concentrations of methyl chloroform can be measured using EPA Method
TO-2 from the Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Air. Compounds which can be determined using this method are nonpolar and highly
volatile organics that can be captured on carbon molecular sieve (CMS) and determined by
thermal desorption techniques. The compounds to be determined by this method have boiling
points in the range of-15° to 120°C (5° to 250°F). Methyl chloroform can be determined using
this method.
In summary, ambient air is drawn through a cartridge containing approximately 0.4 grams
(0.01 ounces) of CMS adsorbent. Methyl chloroform is captured on the adsorbent while major
inorganic compounds pass through. The sample is then capped and sent to the laboratory for
analysis.
7-2
-------
Rotometer
Vent
Dry
Test
Meter
_
Needle
Valve
.
Pump
—• Coupling to
Connect TenGX
Cortridqe
Figure 7-1. EPA Method TO-1 sampling system.1
7-3
-------
.Tenox
•1.5 Grcms (6 cm Bed Depth)
Glcss Wood Plugs
(C.5 cm Long)
Glass Cartridge
(13.5 mm OD x
100 mm Long)
(a) Glass Cartridge
1/2- to
1/8"
Reducing
Union
1/2-
Swagelok
Fitting
Gloss Wool
Plugs
(0.5 cm Long)
1 /5" End Cap •
I— Tenax
-1.5 Grams (7 cm Bed Depth)
Metal Cartridge
(12.7 mm 00 x
100 mm LOng)
(b) Metal Cartridge
Figure 7-2. Tenax® cartridge design.1
7-4
-------
Prior to analysis, the CMS cartridge is purged with 2 or 3 L (0.07 to 0.1 ft3) of pure dry
air to remove any moisture. The cartridge is then heated to 350° to 400°C (660° to 750°F) under
a helium purge, and the desorbed methyl chloroform is collected in a specially designed
cryogenic trap. The collected methyl chloroform is then flash evaporated onto a capillary column
(SE-30) and quantified using a GC/MS system.
The exact run time, flow rate and volume sampled varies from source to source depending
on the expected concentration and the required detection limit. Typically, Method TO-2 is used
when ambient air concentrations are expected to be high. CMS has the ability to adsorb large
quantities of organics before breakthrough occurs. Figure 7-1 is representative of both Methods
TO-1 and TO-2 sampling systems. Figure 7-3 illustrates a CMS trap.
7.3 EPA METHOD TO-141
Ambient air concentrations of methyl chloroform can also be measured using EPA Method
TO-14 from the Compendium of Methods for the Determination of Toxic Organic Compounds
in Ambient Air. This method is based on collection of a whole air sample in SUMMA®
passivated stainless steel canisters and is used to determine semi-volatile and volatile organic
compounds. The compounds are separated by gas chromatography and measured by mass-
selective detector or multidetector techniques such as FID, electron capture detection (ECD), and
photoionization detection (PID). The recommended column for Method TO-14 is an FTP OV-1
capillary with 0.32mm ID. x 0.88 jim cross-linked methyl silicone coating or equivalent.
Samples should be analyzed within 14 days of collection.
This method is applicable to specific semi-volatiles and volatile organic compounds that
have been tested and determined to be stable when stored in pressurized and subatmospheric
pressure canisters. Methyl chloroform can be successfully measured at the parts per billion by
volume (ppbv) level using this method. Figure 7-4 presents a diagram of the canister sampling
system.
7-5
-------
THERMOCOUPLE
STAINLESS
STEEL TUBE
1/4* O.D. x 3" LONG
THERMOCOUPL
CONNECTOR
HEATER
CONNECTOR
END
CAP
Figure 7-3. Carbon molecular sieve trap (CMS) construction.1
7-6
-------
To AC
Inlet
Vacuum/Presure '£
Gauge Xv
Figure 7-4. Canister sampling system.1
7-7
-------
7.4 EPA METHOD 00302
The volatile organic sampling train (VOST) from SW-846, (third edition) is designed for
the collection of volatile organic compounds from the stack gas effluents of hazardous waste
incinerators. The VOST method was designed to collect volatile organics with boiling points in
the range of 30° to 100°C (86° to 212°F). Many compounds with boiling points above 100°C
(212°F) may also be effectively collected using this method. Methyl chloroform concentrations
can be measured using this method. Figure 7-5 presents a schematic of the principle components
of the VOST.
In most cases, 20 L (0.7 ft3) of effluent stack gas are sampled at an approximate flow rate
of 1 L/minute (0.04 ft3/min) using a glass-lined heated probe. The gas stream is cooled to 20°C
(68°F) by passage through a water-cooled condenser and the volatile organics are collected on
a pair of sorbent resin traps. Liquid condensate is collected in the impinger located between the
two resin traps. The first resin trap contains about 1.6 g (0.06 ounce) Tenax® and the second
trap contains about 1 g (0.04 ounce) each of Tenax® and petroleum-based charcoal.
The Tenax® cartridges are then thermally desorbed and analyzed by purge-and-trap
GC/MS along with the condensate catch as specified in EPA Method 5040. Analysis should be
conducted within 14 days of sample collection.
7.5 EPA METHOD 50402
The contents of the sorbent cartridges (collected via VOST, EPA Method 0030) are spiked
with an internal standard and thermally desorbed for 10 minutes at 80°C (176°F) with organic-
free nitrogen or helium gas (at a flow rate of 40 mL/min (2.4 in3)), bubbled through 5 mL (0.3
in3) of organic-free water, and trapped on an analytical adsorbent trap. After the 10 minute
desorption, the analytical adsorbent trap is rapidly heated to 180°C (356°), with the carrier gas
flow reversed so that the effluent flow from the analytical trap is directed into the GC/MS. The
volatile compounds are separated by temperature-programmed gas chromatography and detected
-------
-Heated Probe
Isolation Valves
Carbon Filter
Vacuum
Indicator
Glass Wool
Partlculate
Filter
Thermocouple
Sorbent
Cartridge
Silica Gel
Condenaate
Trap Impinger
^- Exhaust
Figure 7-5. Schematic of volatile organic sampling (rain (VOST).1
-------
by low resolution mass spectrometry. The concentrations of the volatile compounds are
calculated using the internal standard technique.
EPA Methods 5030 and 8240 may be referenced for specific requirements for the thermal
desorption unit, purge-and-trap unit, and GC/MS system. A diagram of the analytical system is
presented in Figure 7-6. The Tenax® cartridges should be analyzed within 14 days of collection.
The desired detection limit of this method is 0.1 ng/L (20 ng per Tenax® cartridge).
7-10
-------
CD
Thermal
Desorption
Chamber
Flow During
Flow to
GC/MS
Heated
Line
Desorption
Flow During
( Adsorption
lie or N2
Analytical Trap
with Heating Coil
(0.3 cm diameter
by 25 cm long)
H20
Purge
Column
©
(?)
Vent
3 % OV-I (1cm)
Tenax (7.7 cm)
{3J Silica Gal (7.7 cm)
(V) Charcoal (7.7 cm)
Figure 7-6. Schematic diagram of trap clesorption/analysis system.2
-------
7.6 REFERENCES FOR SECTION 7.0
1. U.S. Environmental Protection Agency, Compendium of Methods for the Determination
of Toxic Organic Compounds in Ambient Air. EPA/600/4-89/017. Atmospheric Research
and Exposure Assessment Laboratory, Research Triangle Park, NC. June 1988.
2. U.S. Environmental Protection Agency. Test Methods for Evaluating Solid Waste., Third
Edition, Report No. SW-846. Office of Solid Waste and Emergency Response.
Washington, DC. November 1986.
7-12
-------
APPENDIX A
POTENTIAL SOURCE CATEGORIES OF METHYL CHLOROFORM EMISSIONS
A-l
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
1311
1321
1382
1400
1475
1499
2044
2082
2221
2231
2261
2262
2281
2426
2431
2434
2435
2491
2493
2512
2515
2517
2519
2531
Source Description
Crude Petroleum and Natural Gas
Natural Gas Liquids
Oil and Gas Exploration
Nonmetallic Minerals, Except Fuels
Phosphate Rock
Miscellaneous Nonmetallic Minerals
Rice Milling
Malt Beverages
Broadwoven fabric mills, manmade
Broadwoven fabric mills, wool
Finishing plants, cotton
Finishing plants, manmade
Yarn spinning mills
Hardwood dimension and flooring mills
Millwork
Wood kitchen cabinets
Hardwood veneer and plywood
Wood Preserving
Reconstituted wood products
Upholstered household furniture
Mattresses and bedsprings
Wood TV and radio cabinets
Household furniture, nee
Public building and related furniture
(continued)
A-2
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
2541
2591
2599
2611
2653
2655
2672
2674
2721
2732
2752
2754
2761
2782
2789
2796
2800
2812
2813
2816
2819
2821
2822
Source Description
Wood partitions and fixtures
Drapery hardware and blinds and shades
Furniture and fixtures, nee
Pulp mills
Corrugated and solid fiber boxes
Fiber cans, drums and similar products
Paper coated and laminated, nee
Bags: uncoated paper and multiwall
Periodicals
Book printing
Commercial printing, lithographic
Commercial printing, gravure
Manifold business forms
Blankbooks and looseleaf binders
Bookbinding and related work
Platemaking services
Chemicals and Allied Products
Alkalies and Chlorine
Industrial gases
Inorganic Pigments
Industrial Organic Chemicals, nee
Plastics materials and resins
Synthetic rubber
(continued)
A-3
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
2823
2824
2834
2841
2842
2843
2844
2851
2861
2865
2869
2873
2874
2879
2892
2893
2899
2911
3011
3052
3053
3061
3080
Source Description
Cellulosic manmade fibers
Organic fibers, noncellulosic
Pharmaceutical preparations
Soap and other detergents
Polishes and sanitation goods
Surface active agents
Toilet preparations
Paints and allied products
Gum and Wood Chemicals
Cyclic crudes and intermediates
Industrial Organic Chemicals, nee
Nitrogenous Fertilizers
Phosphatic Fertilizers
Agricultural chemicals, nee
Explosives
Printing Ink
Chemical preparations, nee
Petroleum Refining
Tires and inner tubes
Rubber and plastics hose and belting
Gaskets, packing and sealing devices
Mechanical rubber goods
Misc. Plastics Products, nee
(continued)
A-4
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
3081
3082
3086
3087
3089
3211
3229
3231
3241
3251
3253
3255
3264
3272
3274
3275
3292
3295
3296
3299
3312
3313
3315
Source Description
Unsupported plastics film and sheet
Unsupported plastics profile shapes
Plastics foam products
Custom compound purchased resins
Plastics products, nee
Flat glass
Pressed and blown glass, nee
Products of purchased glass
Cement, hydraulic
Brick and Structural Clay Tile
Ceramic wall and floor tile
Clay Refractories
Porcelain electrical supplies
Concrete products, nee
Lime
Gypsum Products
Asbestos products
Minerals, ground or treated
Mineral Wool
Nonmetallic mineral products, nee
Blast furnaces and steel mills
Electrometallurgical products
Steel wire and related products
(continued)
A-5
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
3317
3321
3325
3334
3339
3341
3351
3353
3354
3355
3363
3364
3366
3399
3411
3412
3423
3425
3429
3431
3433
3441
3443
Source Description
Steel pipe and tubes
Gray and Ductile Iron Foundries
Steel foundries, nee
Primary Aluminum
Primary Nonferrous Metals, nee
Secondary Nonferrous Metals
Copper rolling and drawing
Aluminum sheet, plate, and foil
Aluminum extruded products
Aluminum rolling and drawing, nee
Aluminum die-castings
Nonferrous die-casting exc. aluminum
Copper foundries
Primary metal products, nee
Metal cans
Metal barrels, drums, and pails
Hand and edge tools, nee
Saw blades and handsaws
Hardware, nee
Metal Sanitary Ware
Heating equipment, except electric
Fabricated structural metal
Fabricated plate work (boiler shops)
(continued)
A-6
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
3444
3446
3448
3449
3451
3462
3463
3465
3466
3471
3482
3483
3489
3491
3493
3494
3495
3496
3497
3498
3511
3519
3523
Source Description
Sheet metalwork
Architectural metal work
Prefabricated metal buildings
Miscellaneous metal work
Screw machine products
Iron and steel forgings
Nonferrous forgings
Automotive stampings
Crowns and closures
Plating and polishing
Small arms ammunition
Ammunition, exc. for small arms, nee
Ordnance and accessories, nee
Industrial valves
Steel springs, except wire
Valves and pipe fittings, nee
Wire springs
Misc. fabricated wire products
Metal foil and leaf
Fabricated pipe and fittings
Turbines and turbine generator sets
Internal combustion engines, nee
Farm machinery and equipment
(continued)
A-7
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
3524
3531
3532
3533
3534
3535
3536
3537
3541
3542
3545
3546
3548
3549
3553
3554
3555
3556
3559
3561
3563
3564
3565
Source Description
Lawn and garden equipment
Construction machinery
Mining machinery
Oil and gas field machinery
Elevators and moving stairways
Conveyors and conveying equipment
Hoists, cranes, and monorails
Industrial trucks and tractors
Machine tools, metal cutting types
Machine tools, metal forming types
Machine tool accessories
Power-driven handtools
Welding apparatus
Metalworking machinery, nee
Woodworking machinery
Paper industries machinery
Printing trades machinery
Food products machinery
Special industry machinery, nee
Pumps and pumping equipment
Air and gas compressors
Blowers and fans
Packaging machinery
(continued)
A-8
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
3566
3569
3571
3572
3579
3581
3582
3589
3596
3599
3613
3624
3625
3629
3631
3632
3633
3634
3635
3639
3641
3643
3644
Source Description
Speed changers, drives, and gears
General industrial machinery, nee
Electronic computers
Computer storage devices
Office machines, nee
Automatic vending machines
Commercial laundry equipment
Service industry machinery, nee
Scales and balances, exc. laboratory
Industrial machinery, nee
Switchgear and switchboard apparatus
Carbon and Graphite Products
Relays and industrial controls
Electrical industrial apparatus, nee
Household cooking equipment
Household refrigerators and freezers
Household laundry equipment
Electric housewares and fans
Household vacuum cleaners
Household appliances, nee
Electric lamps
Current-carrying wiring devices
Noncurrent-carrying wiring devices
(continued)
A-9
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
3645
3646
3647
3648
3651
3661
3669
3672
3675
3676
3677
3678
3679
3691
3694
3695
3699
3711
3715
3716
3724
3728
3731
Source Description
Residential lighting fixtures
Commercial lighting fixtures
Vehicular lighting equipment
Lighting equipment, nee
Household audio and video equipment
Telephone and telegraph apparatus
Communications equipment, nee
Printed circuit boards
Electronic capacitors
Electronic resistors
Electronic coils and transformers
Electronic connectors
Electronic components, nee
Storage batteries
Engine electrical equipment
Magnetic and optical recording media
Electrical equipment and supplies, nee
Motor vehicles and car bodies
Truck trailers
Motor homes
Aircraft engines and engine parts
Aircraft parts and equipment, nee
Ship building and repairing
(continued)
A-10
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
3732
3743
3751
3761
3764
3769
3792
3795
3799
3812
3821
3823
3824
3825
3826
3827
3829
3841
3842
3861
3873
3900
3914
Source Description
Boat building and repairing
Railroad equipment
Motorcycles, bicycles, and parts
Guided missiles and space vehicles
Space propulsion units and parts
Space vehicle equipment, nee
Travel trailers and campers
Tanks and tank components
Transportation equipment, nee
Search and navigation equipment
Laboratory apparatus and furniture
Process control instruments
Fluid meters and counting devices
Instruments to measure electricity
Analytical instruments
Optical instruments and lenses
Measuring and controlling devices, nee
Surgical and medical instruments
Surgical appliances and supplies
Photographic equipment and supplies
Watches, clocks, watchcases and parts
Miscellaneous Manufacturing Industries
Silverware and plated ware
(continued)
A-ll
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
3931
3944
3949
3951
3952
3953
3961
3993
3995
3996
4111
4226
4491
4499
4512
4581
4741
4789
4911
4925
4939
4952
4953
Source Description
Musical instruments
Games, toys, and children's vehicles
Sporting and athletic goods, nee
Pens and mechanical pencils
Lead pencils and art goods
Marking devices
Costume jewelry
Signs and advertising specialties
Burial caskets
Hard surface floor coverings, nee
Local and suburban transit
Special warehousing and storage, nee
Marine Cargo Handling
Water transportation services, nee
Air transportation, scheduled
Airports, flying fields, and services
Rental of railroad cars
Transportation services, nee
Electric Services
Gas production and/or distribution
Combination utilities, nee
Sewerage Systems
Refuse systems
(continued)
A-12
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
5021
5032
5085
5113
5153
5169
5171
5172
5191
5198
5231
5541
5712
6512
7532
7538
7629
7641
7694
7699
8211
8221
8299
Source Description
Furniture
Brick, stone, and related materials
Industrial Supplies
Industrial and personal service paper
Grain and field beans
Chemicals and allied products, nee
Petroleum bulk stations and terminals
Petroleum products, nee
Farm supplies
Paints, varnishes, and supplies
Paint, glass, and wallpaper stores
Gasoline service stations
Furniture stores
Nonresidential building operators
Top and body repair and paint shops
General automotive repair shops
Electrical repair shops, nee
Reupholstery and furniture repair
Armature rewinding shops
Repair services, nee
Elementary and secondary schools
Colleges and universities
Schools and educational services, nee
(continued)
A-13
-------
TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF
METHYL CHLOROFORM EMISSIONS (continued)
SIC Code
8331
9199
9224
9511
9711
9999
Source Description
Job training and related services
General government, nee
Fire Protection
Air, water, and solid waste management
National security
Nonclassifiable establishments
NEC = not elsewhere classified
Source:
Toxic Chemical Release Inventory (TRI), 1987-1990. On-line access through the databases.
National Library of Medicine, Bethesda, MD.
Crosswalk/Air Toxic Emission Factor Database Management System, Version 1.2. U.S.
Environmental Protection Agency, Research Triangle Park, NC. October 1991.
Volatile Organic Compound (VOC) Paniculate Matter (PM) Speciation Database Management
System, Version 1.4. Research Triangle Park, NC. October 1991.
A-14
-------
APPENDIX B
LISTS OF PAINT, INK, AND PRINTING FACILITIES WITH ANNUAL SALES
GREATER THAN $1 MILLION
B-l
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Aervoe-Pacific Co. Inc.
AExcel Corp.
Agri-Blend Inc.
Akron Paint & Varnish Inc.
Akzo Coatings Inc. Reliance Universal Inc.
Akzo Coatings Inc. Akzo Resins & Vehicles
Akzo Coatings Inc.
Allentown Paint Manufacturing Co.
Also Indus Inc. Morton Paint Co.
Ameritone Paint Corp.
Ameron Inc. Enmar Finishes Div.
Ameron Inc. Ameron Protective Coatings
Div.
Amsterdam Color Works Inc.
Aspen Paints
Atlas Coating Corp.
Automotive Finishes Inc.
Baker Sealants & Coating
Barrett Varnish Co.
Bee Chem Co.
Behr Process Corp.
Benjamin Moore & Co.
Bennette Paint Manufacturing Co.
Best Bros Paint Manufacturing Co.
Beverly Manufacturing Co. (Los Angeles)
Birk Paint Manufacturing Inc.
Blue Ridge Talc Co. Inc.
Brewer Chem Corp.
Brod-Dugan Co.
Bruning Paint Co.
Burkes Paint Co. Inc.
Buten Paint & Wallpaper
Cabot Stains
Cal Western Paint Corp.
Calbar Inc.
California Products Corp.
Carbit Paint Co.
Address
PO Box 485, Gardnerville NV 89410
7373 Production Dr, Mentor OH 44060
PO Box 957, Rowlett TX 75088
1390 Firestone Parkway, Akron OH 44301
1930 Bishop Ln, Louisville KY 40218
21625 Oak St, Matteson IL 60443
1600 Watterson Towers, Louisville KY 40218
PO Box 597, Allentown PA 18105
Box 6208, Canton OH 44706
PO Box 190, Long Beach CA 90801
PO Box 9610, Little Rock AR 72219
201 N Berry St, Brea CA 92621
1546 Stillwell Ave, Bronx NY 10461
1128 SW Spokane St, Seattle WA 98134
820 E 140th St, Bronx NY 10454
6430 Wyoming Ave, Dearborn MI 48126
234 Suydam Ave, Jersey City NJ 07304
1532 S 50th Ct, Cicero IL 60650
2700 E 170th St, Lansing IL 60438
PO Box 1287, Santa Ana CA 92702
51 Chestnut Ridge Rd., Montvale NJ 07645
PO Box 9088, Hampton VA 23670
PO Box 2056, Sinking Spr PA 19608
9118 S Main St, Los Angeles CA 90003
230 Kearny Ave, Jersey City NJ 07305
PO Box 39, Henry VA 24102
PO Box 48, Honolulu HI 96810
2145 Schuetz Rd, St. Louis MO 63146
601 S Haven, Baltimore, MD 21224
727 S 27th St, Washougal WA 98671
5000 Ridge Ave, Philadelphia PA 19128
100 Hale St, Newburyport MA 01950
1 1748 Slauson Ave, Santa Fe Spr CA 90670
2626 N Martha St, Philadelphia PA 19125
PO Box 569, Cambridge MA 02139
927 W Blackhawk St, Chicago IL 60622
Sales in
$ Millions
11
20
1*
4*
300
13
550*
4
o
3
40
15
112
7
4
7*
4
5
o
3
66
33*
370*
5
1
2
2
9
50
15
30
o
5
40
30
5
4
32
5
(continued)
B-2
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Carboline Co.
Cardinal Color Co.
Cardinal Indus Finish Inc.
Century Chem Co.
Certified Coating Products
CF Jameson & Co. Inc.
Charles A Crosbie Labs Inc.
Chemical Technology Labs Inc.
Chemical Coating Corp.
Ciba-Geigy Corp. Drakenfeld Colors
Clement Coverall Inc.
CM Athey Paint Co.
Coatings & Chems Corp.
Colonial Refining & Chem Co.
Columbia Paint Corp.
Columbia Paint Co.
Colwell Gen Inc.
Commercial Chem Co. Inc.
Con-Lux Coatings Inc.
Cook & Dunn Paint Corp. Pure All Paint
Coatings Co.
Cook & Dunn Paint Corp.
Cook & Dunn Paint Corp. Adelphi
Coating
Cook Paint & Varnish Co.
Coronado Paint Co. Inc.
Cosan Chem Corp.
Cotter & Co. Gen Paint & Chem Co.
Courtlaulds Coatings USA Inc.
Cowman & Campbell
CP Inc.
Crest Chem Indus Ltd.
Crosby Coatings Inc.
CWC Indus Inc.
Dalys Inc.
Dampney Co. Inc.
Address
350 Hanley Indus Ct, St. Louis MO 63144
50-56 1st St, Paterson NJ 07524
1329 Potrero Ave, South El Mon CA 91733
5 Lawrence St, Bloomfield NJ 07003
2414 S Connor Ave, Los Angeles CA 90040
PO Box 197, Bradford MA 01835
PO Box 3497, Van Nuys CA 91407
12150 S Alameda St, Lynwood CA 90262
7300 Crider Ave, Pico Rivera CA 90660
PO Box 519, Washington PA 15301
PO Box 557, Camden NJ 08101
1809 Bayard St, Baltimore MD 21230
3067 N Elston Ave, Chicago IL 60618
20575 Ctr Ridge Rd, Cleveland OH 44116
PO Box 2888, Huntington WV 25728
PO Box 4569, Spokane WA 99202
PO Box 329, Fort Wayne IN 46801
PO Box 2126, Santa Ana CA 92707
PO Box 847, Edison NJ 08818
700 Gotham Ave, Carlstadt NJ 07072
700 Gotham Parkway, Carlstadt NJ 07072
700 Gotham Parkway, Carlstadt NJ 07072
PO Box 419389, Kansas City MO 64141
PO Box 308, Edgewater FL 32032
400 14th St, Carlstadt NJ 07072
201 Jandus Rd., Cary IL 60013
PO Box 1439, Louisville, KY 40201
PO Box 70328, Seattle WA 98107
PO Box 333, Connersville IN 47331
PO Box 85, New Lenox IL 60451
PO Box 1038, Chico CA 95927
2686 Lisbon Rd, Cleveland OH 44104
3525 Stone Way N, Seattle WA 98103
85 Paris St, Everett MA 02149
Sales in
$ Millions
65
7
18
5
1
1
1
o
3
o
3
28
4
6
5
3
5
17
20
4
25
8*
20
o
J
100
28
10*
120
160*
3
5
1*
6
5
5
4
(continued)
B-3
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Daniel Products Co.
Davis Paint Co.
Davlin Paint Co. Inc.
DC Tranche & Co.
De Boom Paint Co.
Dean & Barry Co.
Decratrend Paints
Deft Inc.
Del Paint Corp.
Delrac Manufacturers of Bisonite Products
Co. Inc.
DeSoto Inc.
Devoe & Raynolds Co.
Dexter Corp. Dexter Specialty Coatings
Div.
Diamond Products Co. Inc.
DJ Simpson Co.
Dover Sales Co. Inc.
Duncan Enterprises
Dunn Edwards Corp.
Dupli-Color Products Co.
Duralac Inc.
Duron Inc.
Dye Specialties Inc.
Egyptian Lacquer Manufacturing
Ellis & Everard (US Holdings) Inc.
Prillaman Chem Corp.
Elpaco Coatings Corp.
Emco Finishing Products Inc.
Empire State Varnish Co.
Environmental Coatings Inc.
Epoca Co.
Epoxy Coatings Co.
Evans Paint Inc.
Everseal Manufacturing Co. Inc.
Fabrionics Inc.
Address
400 Claremont Ave, Jersey City NJ 07304
1311 Iron St, Kansas City MO 64116
700 Allston Way, Berkely CA 94702
1401 W Wabansia Ave, Chicago IL 60622
645 Texas St, San Francisco CA 94107
296 Marconi Blvd, Columbus OH 43215
251 Mason Way, City of Indu CA 91746
17451 Von Karman Ave, Irvine CA 92714
3105 E Reno St, Oklahoma City OK 73117
PO Box 764, Tonawanda NY 14151
PO Box 5030, Des Plaines IL 60017
PO Box 7600, Louisville KY 40207
1 E Water St, Waukegan IL 60085
709 S 3rd Ave, Marshalltown IA 50158
PO Box 2265, South San Francisco CA 94080
PO Box 2479, Berkeley CA 94702
PO Box 7827, Fresno CA 93747
PO Box 30389, Los Angeles CA 90039
1601 Nicholas Blvd, Elk Grove Vi IL 60007
84 Lister Ave. Newark NJ 07105
10406 Tucker St, Beltsville MD 20705
PO Box 1447, Secaucus NJ 07096
PO Box 4449, Lafayette IN 47903
PO Box 4024, Martinsville VA 24112
PO Box 447, Elkhart IN 46515
470 Cresent St, Jamestown NY 14701
38 Varick St, Brooklyn NY 11222
6450 Hanna Lake SE, Caledonia MI 493 16
5 Lawrence St, Bloomfield NJ 07003
PO Box 1035, Union City CA 94587
PO Box 4098, Roanoke VA 24015
475 Broad Ave, Ridgefield NJ 07657
Route 130 S, Camargo IL 61919
Sales in
$ Millions
20
13
3*
o
J
5
15
17
15
4
3*
408
120*
80
18*
5
3*
30
150*
50
4
150
8
10
96*
8
2
5
5
1
1
4*
12
13
(continued)
B-4
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Parboil Co.
Farwest Paint Manufacturing Co. Inc.
Federated Paint Manufacturing Co.
Ferro Corp. Coatings Div.
Fiber-Resin Corp.
Fine Line Paint Corp.
Finishes Unlimited Inc.
Finnaren & Haley Inc.
Flecto Co. Inc.
Frank W Dunne Co.
Frazee Indus Inc.
Fredericks-Hansen Paint
Fuller O'Brien Corp.
Gilbert Spruance Co.
Given Paint Manufacturing Co. Inc.
GJ Nikolas & Co. Inc.
Glidden Co. Eastern Region
Glidden Co. Southwest Region
Glidden Co. Resin Div.
Gloss-Flo Corp.
Glyptal Inc.
Gordon Bartels Co.
Graham Paint & Varnish Co.
Grow Group Inc. US Paint Div.
Grow Group Inc. Natl Aerosol Products Co.
Grow Group Inc.
Guardsman Products Inc.
Guardsman Chems Inc.
H Behlen & Brother Inc.
Hancock Paint & Varnish
Hanna Chem Coatings Inc.
Harco Chem Coatings Inc.
Harrison Paint Corp.
Hartin Paint & Filler
Hempel Coatings USA
Address
8200 Fischer Rd, Baltimore MD 21222
PO Box 68726, Tukwila WA 98168
1882 S Normal St, Chicago IL 60616
PO Box 6550, Cleveland OH 44101
PO Box 4187, Burbank CA 91503
12234 Los Nietos Rd, Santa Fe Spr CA 90670
PO Box 69, Sugar Grove IL 60554
2320 Haverford Rd, Ardmore PA 19003
PO Box 12955, Oakland CA 94608
1007 41st St, Oakland CA 94608
PO Box 2471, San Diego CA 92112
PO Box 5638, San Bernardino CA 92408
450 E Grand Ave, South San Francisco CA 94080
Richmond St & Tioga St, Philadelphia PA 19134
111 N Piedras St, El Paso TX 79905
2810 Washington Blvd, Bellwood IL 60104
PO Box 15049, Reading PA 19612
PO Box 566, Carrollton TX 75011
1065 Glidden St NW, Atlanta GA 30318
135 Jackson St, Brooklyn NY 11211
305 Eastern Ave, Chelsea MA 02150
2600 Harrison Ave, Rockford IL 61108
4800 S Richmond St, Chicago IL 60632
831 S 21st St, St. Louis MO 63103
2193 E 14th St, Los Angeles CA 90021
200 Park Ave, New York NY 10166
3033 Orchard Vista Dr, Grand Rapids MI 49501
13535 Monster Rd, Seattle WA 98178
Route 30 N Perth Rd, Amsterdam NY 12010
109 Accord Dr, Norwell MA 02061
PO Box 147, Columbus OH 43216
208 DuPont St, Brooklyn NY 11222
PO Box 8470, Canton OH 44711
PO Box 116, Carlstadt NJ 07072
201 Route 17 N, Rutherford NJ 07070
Sales in
$ Millions
11
3
8*
73*
10
5
3
25*
20
7
100
12
140
10
7*
2
140
59
30
4
5
7
10*
30*
5
413
190
6
10
10
25
6
20
3
15
(continued)
B-5
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Hentzen Coatings Inc.
Heresite Protective Coatings Inc.
Hoboken Paint Co. Inc.
Hoffers Inc.
Hy-Klas Paints Inc.
Hydrosol Inc.
ICI Americas Inc. ICI Paints
Illinois Bronze Paint Co.
Indurall Coatings Inc.
Industrial Coatings Intl.
Insilco Corp. Sinclair Paint Co.
International Paint Co. USA Inc.
International Paint Co. USA Inc. Southwest
Div.
International Coatings Co.
Irathane Syss Inc.
IVC Indus Coatings Inc.
J Landau & Co. Inc.
James B Day & Co.
James Bute Co.
Jasco Chem Corp.
John L Armitage & Co.
Johnson Paints Inc.
Jones Blair Co. Oilman Paint &
Wallcovering Div.
Kalcor Coatings Co.
Kaufman Products Inc.
Keeler & Long Inc.
Kelly-Moore Paint Co. Inc. Hurst Div.
Kelly-Moore Paint Co.
King Fiber Glass Corp. Fiber Resin
Supply Div.
Komac Paint Inc.
Kop-Coat Co. Inc.
Kop-Coat Co. Inc. Pettit Paint Co.
Kurfees Coatings Inc.
Address
6937 W Mill Rd, Milwaukee WI 53218
PO Box 250, Manitowoc WI 54221
40 Indus Rd, Lodi NJ 07644
PO Box 777, Wausau WI 54401
1401 S 12th St, Louisville KY 40210
8407 S 77th Ave, Bridgeview IL 60455
925 Euclid Ave, Cleveland OH 44115
300 E Main St, Lake Zurich IL 60047
PO Box 2371, Birmingham AL 35201
7030 Quad Ave, Baltimore MD 21237
6100 S Garfield Ave, Los Angeles CA 90040
6001 Antoine, Houston TX 77091
PO Box 920762, Houston TX 77292
13929 E 166th St, Cerritos CA 90701
PO Box 276, Hibbing MN 55746
PO Box 18163, Indianapolis IN 46218
PO Box 135, Carlstadt NJ 07072
Day Ln, Carpentersville IL 60110
PO Box 1819, Houston TX 77251
PO Drawer J, Mountain View CA 94040
1259 Route 46 E, Parsippany NJ 07054
PO Box 061319, Fort Myers FL 33906
PO Box 1257, Chattanooga TN 37401
37721 Stevens, Willoughby OH 44094
1326 N Bentalov St, Baltimore MD 21216
PO Box 460, Watertown CT 06795
301 W Hurst Blvd, Hurst TX 76053
987 Commercial St, San Carlos CA 94070
366 W Nickerson St, Seattle WA 98119
1201 Osage St, Denver CO 80204
480 Frelinghuysen Ave, Newark NJ 07114
36 Pine St, Rockaway NJ 07866
201 E Market St, Louisville KY 40202
Sales in
$ Millions
12
15
17
47
6
30
843
25
8
14*
100*
50
18
5
8*
9
4
8
3*
7
8*
9
38
6
1*
10
15
230*
2
10
15
11
16
(continued)
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Kwal-Howells Inc.
L & H Paint Products Inc.
Lasting Paints Inc.
Lenmar Inc.
Lilly Chem Products Inc.
Lilly Industrial Coatings Inc.
Lily Co. Inc.
Linear Dynamics Inc.
Lyle Van Patten Co. Inc.
MA Bruder & Sons Inc.
Maas & Waldstein Co.
MAB Paints Inc.
Magruder Color Co. Inc. Radiant Color Div.
Major Paint Co.
Mansfield Paint Co. Inc.
Martec Inc.
Martin-Senour Co.
Mautz Paint Co.
McCormick Paint Works Co.
McWhorter-McCloskey Inc.
Mercury Paint Co. Inc.
Mid-States Paint Co.
Midwest Lacquer Manufacturing Co.
Midwest Paint Manufacturing Co.
Millmaster Onyx Group Inc. Mantrose-
Haeuser Co.
Mobile Paint Manufacturing Co.
Mohawk Finishing Products
Moline Paint Manufacturing Co.
Moling Paint Manufacturing
Monarch Paint Co.
Morton Intl Inc. Norris Paint/TMT
Muralo Co. Inc.
Muralo Co. Inc. Olympic Paint & Chem
Co.
N Siperstein Inc.
Address
PO Box 39-R, Denver CO 80239
PO Box 7311, San Francisco CA 94120
PO Box 4428, Baltimore MD 21223
150 S Calverton Rd, Baltimore MD 21223
PO Box 188, Templeton MA 01468
733 S West St, Indianapolis, IN 46225
PO Box 2358, High Point NC 27261
400 Lanidex Plz, Parsippany NJ 07054
321 W 135th St, Los Angeles CA 90061
PO Box 600, Broomall PA 19008
2121 McCarter Highway, Newark NJ 07104
630 N 3rd St, Terre Haute IN 47808
PO Box 4019, Richmond CA 94804
4300 W 190th St, Torrance CA 90509
169 W Longview Ave, Mansfield OH 44905
760 Aloha St, Seattle WA 98109
101 Prospect Ave, Cleveland OH 44115
PO Box 7068, Madison WI 53707
2355 Lewis Ave, Rockville, MD 20851
5501 E Slauson Ave, Los Angeles CA 90040
14300 Schaefer Highway, Detroit MI 48227
9315 Watson Indus Park, St. Louis MO 63126
9353 Seymour Ave, Schiller Par IL 60176
2313 W River Rd N, Minneapolis MN 55411
500 Post Rd E, Westport CT 06880
4775 Hamilton Blvd, Theodore AL 36582
Route 30 N, Amsterdam NY 12010
5400 23rd Ave, Moline IL 61265
5400 23rd Ave, Moline IL 61265
PO Box 55604, Houston TX 77255
PO Box 2023, Salem OR 97308
PO Box 455, Bayonne NJ 07002
5928 S Garfield Ave, Los Angeles CA 90040
415 Montgomery St, Jersey City NJ 07302
Sales in
$ Millions
23
4
6
13
11
212
30
30
o
3
140*
15
32
30
65
2
o
J
44*
19
18*
5
18
3
5
2
15
45
35*
17
125
29*
5
42
2*
40
(continued)
B-7
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
National Paint Co. Inc.
National Lacquer & Paint Co.
Nelson Tech Coatings Inc.
New York Bronze Powder Co. Inc.
Niles Chem Paint Co.
Norton & Son Inc.
Nu-Brite Chem Co. Inc. Kyanize Paints
O'Brien Corp.
O'Brien Corp. Powder Coatings Div.
O'Brien Corp. Southeast Region
Old Quaker Paint Co.
Orelite Chem Coatings
Pacific Coast Lacquer Co. Inc.
Palmer Paint Products Inc.
Pan Chem Corp.
Paragon Paint & Varnish Corp.
Parker Paint Manufacturing Co.
Parks Corp.
Parks Paint & Varnish Co. Inc.
Passonno Paints
Pave-Mark Corp.
PavePrep Corp.
Perm Color Inc.
Pentagon Chem & Paint Co.
Perfection Paint & Color Co.
Performance Coatings Inc.
Perry & Derrick Co.
Pervo Paint Co.
PFI Incorporated-Paints for Industry
Pierce & Stevens Corp.
Plasti-Kote Co. Inc.
Plasticolors Inc.
Plextone Corp. of America
PMC Inc. Gen Plastics Div.
Ponderosa Paint Manufacturing Co. Inc.
Address
3441 E 14th St, Los Angeles CA 90023
7415 S Green St, Chicago IL 60621
2147 N Tyler Ave, South El Mon CA 91733
519 Dowd Ave, Elizabeth NJ 07201
PO Box 307, Niles MI 49120
148 E 5th St, Bayonne NJ 07002
2nd & Boston St, Everett MA 02149
450 E Grand Ave, South San Francisco CA 94080
5300 Sunrise Rd, Houston TX 77021
PO Box 864, Brunswick GA 31521
2209 S Main St, Santa Ana CA 92707
62 Woolsey St, Irvington NJ 07111
3150 E Pico Blvd, Los Angeles CA 90023
PO Box 1058, Troy MI 48099
1 Washington Ave, Hawthorne NJ 07506
5.49 46th Ave, Long Island NY 11101
PO Box 11047, Tacoma WA 98411
PO Box 5, Somerset MA 02726
660 Tonnelle Ave, Jersey City NJ 07307
500 Broadway, Watervliet NY 12189
PO Box 94108, Atlanta GA 30318
141 Central Ave, Westfield NJ 07090
400 Old Dublin Pike, Doylestown PA 18901
24 Woodward Ave, Ridgewood NY 11385
715 E Maryland St, Indianapolis IN 46202
PO Box 1569, Ukiah CA 95482
2510 Highland Ave, Cincinnati OH 45212
6624 Stanford Ave, Los Angeles CA 90001
921 Santa Fe Springs Rd, Santa Fe Spr CA 90670
710 Ohio St, Buffalo NY 14203
PO Box 708, Medina OH 44258
2600 Michigan Ave, Ashtabula OH 44004
2141 McCarter Highway, Newark NJ 07104
55-T La France Ave, Bloomfield NJ 07003
PO Box 5466, Boise ID 83705
Sales in
$ Millions
o
3
2
2
30
16*
15*
20
150*
40
11*
31
4
o
5
7
5
14*
26
20
3*
10
20
14*
40
16*
6*
3
15
13
2
50
50
17
o
3
4
10
(continued)
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Porter Paint Co.
Potter Paint Co. Inc.
PPG Indus Architectual Finishes Inc.
PPG Indus Inc. Automotive Products Group
Pratt & Lambert Inc.
Pratt & Lambert Inc. Western Div.
Premier Coatings Inc.
Preservative Paint Co. Inc.
Pro-Line Paint Manufacturing Co. Inc.
Proctor Paint & Varnish
Progress Paint Manufacturing Co.
Pruett-Schaffer Chem Co.
Pyrolac Corp.
Quality Coatings Inc.
Raffi & Swanson Inc.
Randolph Products Co.
Red Spot Paint Varnish Co. Red Spot
Westland Inc.
Red Spot Paint Varnish Co.
Reliable Coatings Inc.
Republic Clear Thru Corp.
Republic Powdered Metals Inc.
Riley Bros Inc.
River Valley Coatings Inc.
Riverside Labs Inc.
RJ McGlennon Co. Inc.
Roymal Inc.
RPM Inc.
Rudd Co. Inc.
Rust-Oleum Corp.
Rutland Fire Clay Co.
Sampson Paint Manufacturing Co.
Sampson Coatings Inc.
Sandstrom Products Co.
Saxon Paint & Home Care Centers Inc.
Dreeblan Paint Co.
Address
PO Box 1439, Louisville KY 40201
PO Box 265, Cambridge Ci IN 47327
2233 112th Ave NE, Bellevue WA 98004
PO Box 3510, Troy MI 48007
75 Tonawanda St, Buffalo NY 14207
PO Box 668, Marysville CA 95901
2250 Arthur Ave, Elk Grove Vi IL 60007
5410 Airport Way S, Seattle WA 98108
2646 Main St, San Diego CA 92113
38 Wells Ave, Yonkers NY 10701
PO Box 33188, Louisville KY 40232
PO Box 4350, Pittsburgh PA 15204
55 Schoon Ave, Hawthorne NJ 07506
1700 N State, Chandler IN 47610
100 Eames St, Wilmington MA 01887
Park Place E, Carlstadt NJ 07072
550 S Edwin St, Westland MI 48185
PO Box 418, Evansville IN 47703
13108 Euless St, Euless TX 76040
211 63rd St, Brooklyn NY 11220
PO Box 777, Median OH 44258
860 Washington Ave, Burlington IA 52601
PO Box 580, Aurora IL 60507
411 Union St, Geneva IL 60134
198 Utah St, San Francisco CA 94103
Route 103, Newport NH 03773
PO Box 777, Medina OH 44258
1630 15th Ave W, Seattle WA 98119
11 Hawthorne Parkway, Vernon Hills IL 60061
PO Box 340, Rutland VT 05702
1900 Ellen Rd, Richmond VA 23224
PO Box 6625, Richmond VA 23230
218 S High, Port Byron IL 61275
3729 W 49th St, Chicago IL 60632
Sales in
$ Millions
121
2*
110*
20*
246
10
20
13
7*
20
10
4
4*
2
15
9
15
56
14*
6
15
3
2*
3*
3
4
380
10
89
2
42
9
7
15*
(continued)
B-9
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Schalk Chems Inc.
Scott Paint Corp.
Seagrave Coatings Corp. Clover Leaf Paint
& Varnish
Seaside Inc.
Seibert-Oxidermo Inc.
SEM Products Inc.
Sentry Paint Technologies Inc.
Seymour of Sycamore Inc.
Sheboygan Paint Co.
Sheffield Bronze Paint Corp.
Sherwin-Williams Co.
Sherwin-Williams Co. Automotive Div.
Sherwin-Williams Co. Consumer Div.
Sherwin-Williams Co. Oakland
Sherwin-Williams Co. Chem Coatings Div.
Sigma Coatings Co.
Smiland Paint Co.
Snyder Bros Co.
Southern Coatings Inc.
Southwestern Petroleum Corp.
Spatz Paints Inc.
Specialty Coating & Chem
Spectra-Tone Paint Corp.
Spraylat Corp. Los Angeles
Stanchem Inc.
Standard Detroit Paint Co.
Standard T Chem Co. Inc.
Star Finishing Products Inc.
Star Bronze Co.
STD Coating Corp.
Steelcote Manufacturing Corp.
Sterling Twelve Star Paint
Sterling-Clark-Lurton
Stevens Paint Corp.
Stonhard Inc.
Address
2400 Vauxhall Rd, Union NJ 07083
5940 Palmer Blvd, Sarasota FL 34232
320 Paterson Plank Rd, Carlstadt NJ 07072
PO Box 2809, Long Beach CA 90801
6455 Strong Ave, Detroit MI 48211
120 Sem Ln, Belmont CA 94002
237 Mill St, Darby PA 19023
917 Crosby Ave, Sycamore IL 60178
PO Box 417, Sheboygan WI 53082
17814 S. Waterloo Rd, Cleveland OH 44119
101 Prospect Ave NW, Cleveland OH 44115
101 Prospect Ave NW, Cleveland OH 44115
101 Prospect Ave NW, Cleveland OH 44115
1450 Sherwin Ave, Oakland CA 94608
11541 S Champlain Ave, Chicago IL 60628
PO Box 816, Harvey LA 70059
620 Lamar St, Los Angeles CA 90031
PO Box 760, Toccoa GA 30577
PO Box 160, Sumter SC 29151
PO Box 961005, Fort Worth TX 76161
1439 Hanley Industrial Ct, St. Louis MO 63144
7360 Varna Ave, North Hollywood CA 91605
9635 Klingerman St, South El Mon CA 91733
3465 S La Cienega, Los Angeles CA 90016
401 Berlin St, East Berlin CT 06023
8225 Lyndon Ave, Detroit MI 48238
290 E Joe Orr Rd, Chicago Heights IL 60411
360 Shore Dr, Hinsdale IL 60521
PO Box 2206, Alliance OH 44601
461 Broad Ave, Ridgefield NJ 07657
3418 Gratiot St, St. Louis MO 63103
PO Box 791, Little Rock AR 72203
184 Commercial St, Maiden MA 02148
38 Wells Ave, Yonkers NY 10701
PO Box 308, Maple Shade NJ 08052
Sales in
$ Millions
7
16*
14*
3
11
7
10
10
12
3
2,124
160
170*
32*
250
15
10
7
40
26
5
3
7
5
10
8
14*
15
11
3
4
15
9
15
62
(continued)
B-10
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Strathmore Products Inc.
Sullivan Coatings Inc.
Sunnyside Corp
Superior Varnish & Drier Co.
Superior Sealants Inc.
Supro Corp.
Technical Coatings Laboratory Inc.
Technical Coatings Inc.
Technical Coatings Co.
Tenax Finishing Products
Tera Lite Inc.
Tester Corp.
Thompson & Formby Inc.
Ti-Kromatic Paints Inc.
Tnemec Co. Inc.
Touraine Paints Inc.
Tower Paint Manufacturing
Trail Chem Corp.
Triangle Coatings Inc.
United Paint & Chem Corp.
United Coatings Inc.
United Paint Co.
United Gilsonite Labs
Universal Paint Corp.
Universal Chems & Coatings Inc.
Universe Paint Co.
Valspar Corp. MCI Quality Coatings
Valspar Corp. Colony Paints Div.
Valspar Corp.
Valspar Corp. Masury Paint Co.
Vanex Color Inc.
VJ Dolan & Co. Inc.
Vogel Paint & Wax Inc. Marwin Paints Inc.
Vogel Paint & Wax Inc.
Voplex Corp. Allerton Chem Div.
Address
1970 W Fayette St, Syracuse NY 13204
410 N Hart St, Chicago IL 60622
225 Carpenter Ave, Wheeling IL 60090
PO Box 1310, Merchantville NJ 08109
1135 Sylvan SW, Atlanta GA 30310
2650 Pomona Blvd, Pomona CA 91768
PO Box 565, Avon CT 06001
PO Box 3337, Austin TX 78764
1000 Walsh Ave, Santa Clara CA 95050
390 Adams St, Newark NJ 07114
1631 S 10th St, San Jose Ca 95112
620 Buckbee St, Rockford IL 61106
825 Crossover Ln, Memphis TN 38117
2492 Doswell Ave, St. Paul MN 55108
PO Box 411749, Kansas City MO 64141
1760 Revere Beach Parkway, Everett MA 02149
620 W 27th St, Hialeah FL 33010
9904 Gidley St, El Monte CA 91731
1930 Fairway Dr, San Leandro CA 94577
24671 Telegraph Rd, Southfield Ml 48034
2850 Festival Dr, Kankakee IL 60901
404 E Mallory, Memphis TN 38109
PO Box 70, Scranton PA 18501
PO Box 1218, La Puente CA 91749
1975 Fox Ln, Elgin IL 60123
PO Box 668, Marysville CA 95901
6110 Gunn Highway, Tampa FL 33625
PO Box 418037, Kansas City MO 64141
1101 S 3rd St, Minneapolis MN 55415
1401 Severn St, Baltimore MD 21230
1700 Shawnee St, Mount Vernon IL 62864
1830 N Laramie Ave, Chicago IL 60639
2100 N 2nd St, Minneapolis MN 55411
Industrial Air Park Rd., Orange City I A 51041
763 Linden Ave, Rochester NY 14625
Sales in
$ Millions
6
2*
14
7*
11*
4
6
8
6
6*
3
43*
44*
3
50
17
10
4
5
11*
65
25
22*
20
10
3*
12
15
527
8
4
5
8*
100
1
(continued)
B-ll
-------
TABLE B-l.
PAINT AND ALLIED PRODUCTS FACILITIES (SIC 2851) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Waterlox Chem & Coatings Corp.
Watson-Standard Co. Jordan Paint
Manufacturing Co.
Watson-Standard Co.
Wattyl Group Precision Paint Group
WC Richards Co. Inc.
Welco Manufacturing Co. Inc.
Wellborn Paint Manufacturing Co.
Western Automotive Finishes
Westfield Coatings Corp.
Westinghouse Elec Corp. Insulating
Materials Div.
Whittaker Corp. Whittaker Decatur Coatings
William Zinsser & Co.
Wiltech Corp.
Wisconsin Protective Coatings Corp.
WM Barr & Co. Inc.
Yenkin Majestic Paint Corp.
Zehrung Corp
Zolatone Process Inc.
ZPC Indus Coatings Inc.
Zynolyte Products Co.
Address
9808 Meech Ave, Cleveland OH 44105
7250 Franklin St, Forest Park IL 60130
PO Box 11250, Pittsburgh PA 15238
5275 Peachtree, Atlanta GA 30341
3555 W 123rd St, Blue Island IL 60406
1225 Ozark St, North Kansas MO 64116
215 Rossmoor Rd SW, Albuquerque NM 87102
1450 Ave R, Grand Prairi TX 75050
PO Box 815, Westfiled MA 01086
Route 993, Manor PA 15665
PO Box 2238, Decatur AL 35602
31 Belmont Dr, Somerset NJ 08873
PO Box 517, Longview WA 98632
PO Box 216, Green Bay WI 54305
PO Box 1879, Memphis TN 38113
PO Box 369004, Columbus OH 43236
3273 Casitas Ave, Los Angeles CA 90039
3411 E 15th St, Los Angeles CA 90023
120 E Minereal St, Milwaukee WI 53204
PO Box 6244, Carson CA 90749
Sales in
$ Millions
4
4
29*
15
15*
10
15
17*
7
15
12*
16
2
10
95
80
2*
6
2
25
* Indicates an estimated financial figure.
Source: Gale Research, Inc. Ward's Business Directory of U.S. Private and Public Companies-1991, Volume 4.
Detroit, MI. 1991.
B-12
-------
TABLE B-2.
PRINTING INK MANUFACTURING FACILITIES (SIC 2893) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Acme Printing Ink Co. Packaging Inc. Corp.
Acme Printing Ink Co.
AJ Daw Printing Ink Co.
American Inks & Coatings Corp.
Autoroll Machine Corp.
BASF Corp. Coatings & Colorants Div.
Bomark Inc.
Borden Inc. Coatings & Graphics Group
Braden Sutphin Ink Co.
Celia Corp.
Central Ink & Chem
Colonial Printing Ink Corp
Converters Ink Co.
Croda Inks Corp.
Custom Chem Corp.
Del Val Ink & Color Co. Inc.
Excello Color & Chem
Flint Ink Corp.
Flint Ink Corp. Capitol Printing Ink
Flint Ink Corp.
Cans Ink & Supply Co. Inc.
Gotham Ink & Color Co. Inc.
Graphic Color Corp.
Handschy Ink & Chems Inc.
Ink Masters Inc.
James River Corp. of Virginia CZ Inks Div.
JM Huber Corp. Carbon Div.
Kerley Ink Engineers Inc.
Kohl & Madden Printing Ink Corp.
Lakeland Laboratory Inc. Alfa Ink Div.
Lakeland Laboratory Inc.
Lawter Intl Inc.
Merit Printing Inc. Co.
Address
5001 S Mason Ave, Chicago IL 60638
165 Bond St, Elk Grove Vi IL 60007
3559 S Greenwood Ave, Los Angeles CA 90040
PO Box 803, Valley Forge PA 19482
11 River St, Middleton MA 01949
1255 Broad St, Clifton NJ 07015
601 S 6th Ave, City of Indu CA 91746
630 Glendale - Milford, Cincinnati OH 45215
3650 E 93rd St, Cleveland OH 44105
320 Union St, Sparta MI 49345
1100 N Harvester Rd, West Chicago IL 60185
180 E Union Ave, East Rutherford NJ 07073
1301 S Park Ave, Linden NJ 07036
7777 N Merrimac, Niles IL 60648
30 Paul Kohner PI, Elmwood Park NJ 07407
1301 Taylors Ln, Riverton NJ 08077
1446 W Kinzie St, Chicago IL 60622
25111 Glendale Ave, Detroit MI 48234
806 Charming PI ME, Washington DC 20018
1404 4th St, Berkeley CA 94710
1441 Boyd St, Los Angeles CA 90033
5-19 47th Ave, Long Island NY 11101
750 Arthur Ave, Elk Grove Vi IL 60007
120 25th Ave, Bellwood IL 60104
2842 S 17th Ave, Broadview IL 60153
4150 Carr Ln, St. Louis MO 63119
9300 Needlepoint Rd, Baytown TX 77521
2839 19th Ave, Broadview IL 60153
222 Bridge Plz Sq, Hackensack NJ 07601
655 Washington Ave, Carlstadt NJ 07072
655 Washington Ave, Carlstadt NJ 07072
990 Skokie Blvd, Northbrook IL 60062
1451 S Lorena St, Los Angeles CA 90023
Sales in
$ Millions
100
140*
13
15
12
105*
3
17*
25
15
9
17
16*
32*
40
5
84*
235
23
30*
18
4
18
30
3
28
18*
4*
45
2*
3
136
4*
(continued)
B-13
-------
TABLE B-2.
PRINTING INK MANUFACTURING FACILITIES (SIC 2893) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Name
Midland Color Co.
Miller-Cooper Co.
Morrison Printing Ink Co.
Naz-Dar Co.
Nor-Cote Intl Inc.
North American Printing Ink
Northern Printing Ink Corp.
Polypore Inc.
Polytex Color & Chem
PPG Indus Inc. PPG Ink Products Co.
Rexart Chem Corp.
Ron Ink Co. Inc.
Sicpa Indus of America Inc.
Sinclair & Valentine LP
Sun Chem Corp.
Sun Chem Corp. Gen. Printing Ink Div.
Superior Printing Ink Co. Inc.
United States Printing Ink Corp. Leber Ink
Div.
United States Printing Ink Corp.
Van Son Holland Corp. of America
Vivitone Inc.
Walter W Lawrence
Wikoff Color Corp.
Address
651 Bonnie Ln, Elk Grove Vi IL 60007
1601 Prospect Ave, Kansas City MO 64127
4801 W 160th St, Cleveland OH 44135
1087 N Northbranch St, Chicago IL 60622
PO Box 668, Crawfordsville IN 47933
1524 David Rd, Elgin IL 60123
8360 10th Ave N, Minneapolis MN 55427
4601 S 3rd Ave, Tucson AZ 85714
820 E 140th St, Bronx NY 10454
1835 Airport Exchange Blvd, Covington KY 41018
1183 Westside Ave, Jersey City NJ 07306
61 Halstead St, Rochester NY 14610
8000 Research Way, Springfield VA 22153
2520 Pilot Knob Rd, St. Paul MN 55120
PO Box 1302, Fort Lee NJ 07024
135 W Lake St, Northlake IL 60164
70 Bethune St, New York NY 10014
PO Box 88700, Seattle WA 98138
343 Murray Hill Pkwy, East Rutherford NJ 07073
92 Union St, Mineola NY 11501
110 E 27th St, Paterson NJ 07514
9715 Alpaca St, South El Mon CA 91733
PO Box W, Fort Mill SC 29715
Sales in
$ Millions
85
6
14*
15*
5
14
8
10
o
5
15
6*
7
25
186
1,100
410*
50
6
65
42
8
1
45*
indicates an estimated financial figure.
Source: Gale Research, Inc. Ward's Business Directory of U.S. Private and Public Companies-1991, Volume 4.
Detroit, MI. 1991.
B-14
-------
TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
2711 Newspapers
Advance Publications Inc.
Affiliated Publications Inc.
Chicago Tribune Co.
Cox Enterprises Inc.
Dow Jones & Co. Inc.
EW Scripps Co.
Freedom Newspapers Inc.
Gannett Co. Inc.
Hearst Corp.
Ingersoll Publications Co.
Knight-Ridder Inc.
Media Gen Inc.
New York Times Co.
News America Publishing Inc.
Thomson Newspapers Corp.
Times Mirro Co.
Tribune Co.
Location
Staten Island, NY
Boston, MA
Chicago, IL
Atlanta, GA
Washington, DC
Wilmington, DE
Irvine, CA
Arlington, VA
New York, NY
Princeton, NJ
Miami, FL
Richmond, VA
New York, NY
New York, NY
Des Plaines, IL
Los Angeles, CA
Chicago, IL
Sales (millions)
2,200*
542
500
1,970
1,444
1,266
500
3,518
1,900*
1,010*
2,268
606
1,769
3,000
550*
3,475
2,455
2721 Periodicals
ABC Publishing
Billboard Publications Inc.
BPI Communications Inc.
Cahners Publishing Co. New York Magazine
Div.
Chiton Co.
CMP Publications Inc.
Conde Nast Publications Inc.
New York, NY
New York, NY
New York, NY
New York, NY
Radnor, PA
Manhasset, NY
New York, NY
310*
100
105
102
150
187*
280*
(continued)
B-15
-------
TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC
ANNUAL SALES GREATER THAN $1 MILLION
27) WITH
(continued)
Company
Grain Communicating Inc.
Diamonds Communications Inc.
Edgell Communications Inc.
Forbes Inc.
International Data Group Inc.
Meredith Corp.
Meredith Corp. Ladies' Home Journal
National Enquirer Inc.
National Geographic Soc.
Newsweek Inc.
Official Airline Guides Inc.
Penthouse Intl. Ltd.
Penton Publishing Inc.
Peterson Publishing Co.
Playboy Enterprises Inc.
Reader's Digest Assn. Inc.
Reed Publishing (USA) Inc. Cahners Publishing
Co.
Reed Publishing (USA) Inc.
Rodale Press Inc.
Scholastic Inc.
Simon & Shuster Inc. Bur of Bus Practice
Standard & Poor's Corp.
Thompson Corp. Thompson Bus. Info.
Time Inc. Magazine Co.
Times Mirror Magazines Inc.
Location
Chicago, IL
New York, NY
Cleveland, OH
New York, NY
Framingham, MA
Des Moines, IA
New York, NY
Lantana, FL
Washington, DC
New York, NY
Oak Brook, IL
New York, NY
Cleveland, OH
Los Angeles, CA
Chicago, IL
Pleasantville, NY
Newton, MA
Newton, MA
Emmaus, PA
New York, NY
Waterford, CT
New York, NY
Stamford, CT
New York, NY
New York, NY
Sales (millions)
145
470*
205
200
500
792
100
180
425
256
130*
160*
151
140*
160
1,832
430
600
150*
250*
100*
260*
160*
1,500*
470*
(continued)
B-16
-------
TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
Trader Publications Inc.
US News & World Report Inc.
Warren Gorham & Lament Inc.
Whittle Communications Inc.
Ziff Communications Co.
Ziff Communications Co. Zif-Davis Publishing
Co.
Location
Clearwater, FL
New York, NY
New York, NY
Knoxville, TN
New York, NY
New York, NY
Sales (millions)
270*
140*
130
210*
340*
160*
2731 Book Publishing
Addison-Wesley Publishing Co.
Bantam Doubleday Dell Publishing Group Inc.
David C. Cook Publishing Co.
Encyclopedia Britannica Inc.
Field Publications
Grolier Inc.
Harcourt Brace Jovanovich Inc.
Harper Collins Publishers Inc.
Houghton Mifflin Co.
Insilco Corp.
John Wiley & Sons Inc.
Lawyers Co-Operative Publishing Co. Inc.
Macmillan Inc.
Macmillan Inc. Info Svcs & Instruction
MacMillan Intl. Inc.
Macmillan-McGraw-Hill School Publishing Co.
School Div.
Reading, MA
New York, NY
Elgin, IL
Chicago, IL
Middletown, CT
Danbury, CT
Orlando, FL
New York, NY
Boston, MA
Midland, TX
New York, NY
Rochester, NY
New York, NY
New York, NY
New York, NY
New York, NY
120*
180*
100
624
100*
440*
1,341
450
370
450*
282
150*
950*
416
146*
200
(continued)
B-17
-------
TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
Macmillian-McGraw-Hill School Publishing Co.
McGraw-Hill Inc. McGraw-Hill Intl Book Group
Mosby Year Book Inc.
Prentice Hall Inc.
Putnam Publishing Group, Inc.
Rand McNally & Co.
Random House, Inc.
RR Donnelley & Sons Co. Willard Div.
Simon & Schuster Inc.
South- Western Publishing Co.
Sunday School Bd of the Southern Baptist
Convention
Time-Life Books Inc.
West Publishing Co.
Western Publishing Group Inc.
World Book Inc.
Zondervan Corp.
Location
Lake Forest, IL
New York, NY
St. Louis, MO
New York, NY
New York, NY
Skokie, IL
New York, NY
Willard, OH
New York, NY
Cincinnati, OH
Nashville, TN
Alexandria, VA
St. Paul, MN
Racine, WI
Chicago, IL
Grand Rapids, MI
Sales (millions)
390*
115
150
970*
100
430*
325
150
1,320
112
172
350
450*
480
330*
100*
2732 Book Printing
Arcata Graphics Co. Arcata Graphics Book
Group
Banta Corp.
Bertelsmann Printing & Mfg. Corp.
Brown Printing Co. (Waseca Minnesota)
Great Lakes Color Printing Corp.
Harper & Row Publishers
Kingsport, TN
Menasha, WI
Berryville, VA
Waseca, MN
Brentwood, TN
New York, NY
170*
568
220*
363
210*
450
(continued)
B-18
-------
TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
Jostens Inc. Printing & Publishing Div.
RR Donnelley & Sons Co.
Location
Minneapolis, MN
Chicago, IL
Sales (millions)
121
3,122
2741 Misc Publishing
Commerce Clearing House Inc.
Donnelley Directory
GTE Telephone Operations Inc. GTE Directories
Corp.
McGraw-Hill Info. Svcs. Co.
NYNEX Info Resources Co.
RL Polk & Co.
Simplicity Holdings, Inc.
Simplicity Pattern Co.
Southwestern Bell Yellow Pages Inc.
Southwestern Bell Publications Inc.
U.S. West Direct (U.S. West Marketing
Resources Group Inc.)
Wonderland Music Co. Inc.
Riverwoods, IL
New York, NY
Dallas-Fort, TX
New York, NY
Middleton, MA
Detroit, MI
New York, NY
New York, NY
St. Louis, MO
St. Louis, MO
Aurora, CO
Burbank, CA
678
1,300*
360*
668
800
280
110*
101
240*
280*
160*
200*
2752 Commercial Printing-Lithographic
American Signature Graphics Foote & Davies
Div.
American Bank Stationary Co.
Avery Intl Corp. Avery Label Co.
Graphic Controls Corp.
Graphisphere Corp.
HS Crocker Co. Inc.
Judd's Inc.
NMG Inc.
Atlanta, GA
Baltimore, MD
Azusa, CA
Buffalo, NY
Des Plaines, IL
South San Francisco, CA
Washington, DC
Los Angeles, CA
195
110*
110*
140
110
140*
114
105
(continued)
B-19
-------
TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
Perry Printing Corp.
Quebecor Printing (USA) Inc.
Queens Group Inc.
Ringler America Inc.
RR Donnelley & Sons Co. Mattoon Mfg. Div.
RR Donnelley & Sons Co. Lancaster Mfg. Div.
Shea Communications Co.
Taylor Corp.
Treasure Chest Advertising Co. Inc.
Valassis Inserts Inc.
World Color Press Inc.
Location
Waterloo, WI
St. Paul, MN
Long Island, NY
Itasca, IL
Mattoon, IL
Lancaster, PA
Louisville, KY
Mankato, MN
Glendora, CA
Livonia, MI
Effingham, IL
Sales (millions)
175
770
100
700
110*
190*
120
540*
550*
400*
650
2754 Commercial Printing-Gravure
All-State Legal Supply Co.
Arcata Graphics Co.
Beck Co. (Langhorne Pennsylvania)
Clark Printing Co. Inc.
ColorArt Inc.
Dennison Mfg. Co. IPC Dennison Co.
Dinagraphics Inc.
Golden Belt Mfg. Co.
Graphic Ctr. Cos. Inc. Blake Printery
International Label Co.
JW Fergusson & Sons
Maxwell Communications Corp. Atglen
McCleery -Gumming Co.
Cranford, NJ
Baltimore, MD
W, Langhorne, PA
North Kansas, MO
St. Louis, MO
Rogersville, TN
Cincinnati, OH
Durham, NC
St. San Luis Obi, CA
Clarksville, TN
Richmond, VA
Atglen, PA
Washington, IA
43
500*
10
14*
30
60
20
70
11
30
34
50*
22
(continued)
B-20
-------
TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
Meredith-Burda Corp.
Perry Printing Corp. Norway Div.
Printing House Inc. (Quincy Florida)
Ringier America Inc. Corinth Div.
Sheridan Press
Southern Gravure Svc. Inc.
Stevens Graphics Inc.
Technographic Inc. Decotone
World Color Press Inc. Salem Gravure Div.
Location
Des Moines, IA
Norway, MI
Quincy, FL
Corinth, MS
Hanover, PA
Louisville, KY
Atlanta, GA
Lexington, SC
Salem, IL
Sales (millions)
500
25*
24
80
15
58*
150
30
80
2759 Commercial Printing Nee
Alden Press Inc.
Avery Intl. Corp. Soabar Products Group
Bowne & Co. Inc.
Curtis 1000 Inc.
Data Documents Inc. (Omaha)
Deluxe Corp.
Duplex Products Inc.
Graphic Indus. Inc.
John H. Harland Co.
Maxwell Commun Corp.
Meehan-Tooker Inc.
Quad Graphics Inc.
RR Donnelley & Sons Co. Warsaw Mfg. Div.
Webcraft Technologies Inc.
Williamhouse-Regency Inc.
Elk Grove Village, IL
Philadelphia, PA
New York, NY
Atlanta, GA
Omaha, NE
St. Paul, MN
Sycamore, IL
Atlanta, GA
Atlanta, GA
St. Paul, MN
East Rutherford, NJ
Pewaukee, WI
Warsaw, IN
North Brunswick, NJ
New York, NY
170*
100*
190
160*
200
1,316
327
310
345
720*
110
380
160*
220*
230
(continued)
B-21
-------
TABLE B-3.
PRINTING AND PUBLISHING FACILITIES (SIC 27) WITH
ANNUAL SALES GREATER THAN $1 MILLION (continued)
Company
World Color Press Inc. Spartan Printing Co.
Location
Sparta, IL
Sales (millions)
100*
2761 Manifold Business Forms
Allied Paper Inc. Allied-Energy Syss Inc.
American Bus Products Inc.
Arnold Corp.
CST Group Inc.
Ennis Bus. Forms Inc.
McGregor Printing Corp.
Moore Corp. Ltd. Moore Bus. Forms & Syss.
Div.
New England Bus. Svc. Inc.
Office Electronic Inc.
Standard Register Co.
Uarco Inc.
Vanier Graphics Corp. (American Bus. Products
Inc.)
Wallace Computer Svcs. Inc.
Dayton, OH
Atlanta, GA
Dayton, OH
Wheeling, IL
Ennis, TX
Washington, DC
Glenview, IL
Groton, MA
Itasca, IL
Dayton, OH
Barrington, IL
Santee, CA
Hillside, IL
130*
387
200
110
130
125
1,675
226
105
709
520*
133
429
2771 Greeting Cards
American Greetings Corp.
American Greetings Corp. Seasonal Div.
Current Inc. (Colorado Springs Colorado)
Gibson Greetings Inc.
Hallmark Cards Inc.
Hallmark Cards Inc. Topeka Products
Cleveland, OH
Oscoola, AR
Colorado Springs, CO
Cincinnati, OH
Kansas City, MO
Topeka, KS
1,309
110
160
463
2,500
120*
* Indicates an estimated financial figure
Source: Gale Research, Inc. Ward's Business Directory of U.S. Private and Public Companies-1991, Volume 4.
Detroit, MI. 1991.
B-22
-------
APPENDIX C
SUMMARY OF EMISSION FACTORS
LISTED IN THIS DOCUMENT
C-l
-------
TABLE C-l.
SUMMARY OF METHYL CHLOROFORM EMISSION FACTORS
SIC
2869
2869
2869
2869
2869
SIC Description
Industrial Organic Compounds
Industrial Organic Compounds
Industrial Organic Compounds
Industrial Organic Compounds
Industrial Organic Compounds
sec
301125
30112528
30112528
30112525
30112525
SCC Description
Chemical Manufacturing
1,1,1 -Trichloroethane
Chemical Manufacturing
1,1,1 -Trichloroethane
Distillation Column Vent
Chemical Manufacturing
1,1,1 -Trichloroethane
Distillation Column Vent
Chemical Manufacturing
Chemical Manufacturing
Emission Factor
1.2200 Ib/ton methyl
chloroform produced
0.720 kg/metric ton methyl
chloroform produced
0.003 kg/metric ton methyl
chloroform produced
9.00 kg/metric ton methyl
chloroform produced
0.500 kg/metric ton methyl
chloroform produced
Quality
Rating3
U
E
E
E
E
Reference
4-13
4-13
4-13
4-13
4-13
Note
Methyl chloroform handling
Emissions from loading and
unloading of tanks and tank
cars
Uncontrolled
Controlled with incinerator
Heat transfer unit/production
by hydrochlorination
Separation unit/production by
hydrochlorination
aUnratable due to insufficient information.
-------
TABLE C-2.
SUMMARY OF VOC EMISSION FACTORS*
SIC
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
SIC Description
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
sec
30112529
30112529
30112529
30112529
30112529
30112529
30112529
30112529
30112529
30112529
SCC Description
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
1,1,1-Trichloroethane Mfg. -
Fugitives
Emission Factor
0.104 kg/hr/source
0.00083 kg/hr/source
0.0017 kg/hr/source
0.015 kg/hr/source
0.0056 kg/hr/source
0.0071 kg/hr/source
0.00023 kg/hr/source
0.0494 kg/hr/source
0.0214 kg/hr/source
0.228 kg/hr/source
Quality
Rating3
U
U
U
U
U
U
U
U
U
U
Reference
4-15
4-15
4-15
4-15
4-15
4-15
4-15
4-15
4-15
4-15
Note
Fugitives-Gas/vapor pressure relief seals
Fugitives-Flanges
Fugitives-Open ended lines
Fugitives-Sampling connections
Fugitives-Gas valves
Fugitives-Light liquid valves
Fugitives-Heavy liquid valves
Fugitives-Light liquid pump seals
Fugitives-Heavy liquid pump seals
Fugitives-Gas/Vapor compressor seals
*Note: To obtain methyl chloroform leak emission factor for each component, multiply VOC emission factor above by the fraction of methyl chloroform in the stream.
aBased on engineering judgement.
-------
TECHNICAL REPORT DATA
fHcasc read Instructions on the reverse before completing!
1. REPORT NO.
4. TITLC AND SUBTITLE
Locating And Estimating Air Emissions From Sources Of
Methyl Chloroform
6. PERFORMING ORGANIZATION CODE
3 RtCIP"'MT'S ACCESSION NO.
REPOF1T DATF
October 1993
'. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
TRC Environmental Corporation
100 Europa Drive, Suite 150
Chapel Hill, INC 27514
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D9-0173
12. SPONSORING AGENCY NAME AND ADDRESS
U. S. Environmental Protection Agency
OAR, OAQPS, TSD, EIB, EFMS (MD-14)
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer: Dennis Beauregard
16. ABSTRACT
To assist groups interested in inventorying air emissions of various potentially toxic
substances, EPA is preparing a series of documents such as this to compile available
information on sources and emission of these substances. This document deals
specifically with Methyl Chloroform. Its intended audience includes federal, State
and local air pollution personnel and others interested in locating potential emitters
of Methyl Chloroform and in making gross estimates of air emissions therefrom.
This document presents information on(l) the types of sources that may emit Methyl
Chloroform, (2) process variations and release points for these sources, and (3)
available emissions information indicating the potential for Methyl Chloroform releases
into the air from each operation.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Methyl Chloroform
Air Emissions Sources
Locating Air Emissions Sources
Toxic Substances
Emission Estimation
8. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (Tills Report)
Unclassified
21 . NO. OF PAGES
144
20. SECURITY CLASS (Tins page)
Unclassified
EPA Form 2220-1 (R«v. 4—77) PREVIOUS EDITION is OBSOLETE
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