United States
Environmental Protection
Agency
Office of Air Quality
Pinning and Standards
Research Trianjle Park. NC 27711
EPA-454/R-93-006
February 1993
ZE
LOCATING AND ESTIMATING
AIR EMISSIONS
FROM SOURCES OF
METHYLENE CHLORIDE
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LOCATING AND ESTIMATING AIR EMISSIONS
FROM SOURCES OF METHYLENE CHLORIDE
Final Report
Prepared for:
Dallas Safriet
Emission Inventory Branch
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Prepared by:
Radian Corporation
Post Office Box 13000
Research Triangle Park, North Carolina 27709
April 22, 1993
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This report has been reviewed by the Office Of Air Quality Planning
And Standards, U.S. Environmental Protection Agency, and has been
approved for publication. Any mention of trade names or commercial
products is not intended to constitute endorsement or recommendation
for use.
EPA-454/R-93-006
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TABLE OF CONTENTS
Section Page
1 Purpose of Document 1
References for Section 1 4
2 Overview of Document Contents 5
3 Background 7
Nature of Pollutant 7
Overview of Production and Use 9
References for Section 3 13
4 Emissions from Methylene Chloride Production 15
Process Descriptions 15
Emission Sources and Controls 20
Emission Estimates 25
References for Section 4 36
5 Emissions from Uses of Methylene Chloride 37
Paint Stripper Industry 37
References for Paint Stripper Industry 53
Plastics Manufacturing 55
Polycarbonate Resins 55
Triacetate Fiber 64
Plastics Production 68
References for Plastics Manufacturing 72
Flexible Urethane Foam Production Industry 73
References for Polyurethane Foam Industry 81
Pharmaceutical Manufacturing 83
References for Pharmaceutical Manufacturing .... 97
Solvent Cleaning and Photoresist Stripping 99
References for Solvent Cleaning and Photoresist
Stripping 120
Aerosol Packaging and Dispensing 121
11
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TABLE OF CONTENTS (Continued)
Section Page
References for Aerosol Packaging and Dispensing . . 132
Miscellaneous 135
Pesticide Manufacturing 135
Photographic Film Manufacture 138
Paints and Coatings 141
References for Miscellaneous Section 143
6 Source Test Procedures 145
EPA Method 0030 145
EPA Methods 5040 And 5041 147
EPA Method 18 149
Compendium Methods TO-1, TO-2, and TO-14 151
NIOSH Method 1005 153
References for Section 6 154
APPENDICES
Appendix Page
A Example Procedures to Estimate Methylene Chloride Emissions A-l
References for Appendix A A-8
B National List of Paint Stripper Formulators (July 1987) . B-l
C National List of Aerosol Packagers C-l
D TRIS List of Pharmaceutical Facilities Using Methylene
Chloride D-l
E Calculation of Uncontrolled Open-Top Vapor Cleaner Emission
Factor Incorporating Recycle E-l
111
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LIST OF TABLES
Table Page
1 Chemical and Physical Properties of Methylene Chloride . . 8
2 Estimated United States Methylene Chloride Consumption By End
Use for 1991 [in Mg (Million Pounds)] 11
3 Potential Source Categories of Methylene Chloride Emissions 12
4 United States Methylene Chloride Production 16
5 Control Techniques And Efficiencies Applicable to Equipment
Leak Emissions 22
6 Waste and Wastewater Emission Control Techniques and
Efficiencies 26
7 1983 Reported Controls and Control Efficiencies from
Facilities
8
9
10
Producing Methylene Chloride
Average Emission Factors for Equipment Leak Emissions . . .
Emission Factors for Methylene Chloride Production . . . .
Methylene Chloride Consumption in 1987 by Paint Stripper
Sector .
27
. 32
. 34
39
11 Control Techniques for Emissions of Chlorinated Solvents from
Paint Stripper Formulators 44
12 Estimated Methylene Chloride Emissions from Paint Stripper
Formulators (1988) 46
13 Estimated Methylene Chloride Emissions From Automobile
Manufacturing Facilities, 1987 48
14 Estimated Methylene Chloride Emissions From Large-Scale
Military Users of Paint Stripper, 1987 50
15 Paint Stripping Emissions Factors 51
16 Additional Control Techniques for Emissions of Methylene
Chloride Solvents from Paint Stripper Users 52
17 Estimated 1983 Emissions and Controls at Facilities Using
Methylene Chloride in Polycarbonate Resin Production ... 59
18 Estimated Methylene Chloride Emissions and Controls Associated
with Triacetate Fiber Manufacture 67
19 Estimated Methylene Chloride Emissions and Controls Associated
with Plastics Production at General Electric, Pittsfield,
Massachusetts in 1983 69
20 Uncontrolled Emission Factors for Polyurethane Foam Production
IV
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LIST OF TABLES (Continued)
Table Page
21 Control Techniques and Efficiencies Used to Estimate
Controlled Emissions from Polyurethane Flexible Foam
Production 79
22 Partial List of Pharmaceutical Manufacturing Facilities that
Use Methylene Chloride 84
23 Methylene Chloride Purchases and Ultimate Disposition
by Pharmaceutical Manufacturers 91
24 Methylene Chloride Emission Factors for
Pharmaceutical Manufacturing 92
25 Available Control Techniques for OTVC Operations .... 113
26 Available Control Techniques for In-Line Operations . . . 114
27 Available Control Techniques for Cold Cleaners 115
28 Methylene Chloride Usage and Emission Factors for Uncontrolled
and Controlled Cleaners 117
29 National Emissions of MC From Organic Solvent Cleaners, (1983738
30 Weight Percent of Methylene Chloride in Aerosol Product Tanks,
Reported by Section 114 Questionnaire Respondents (1987) 123
31 Control Techniques for Emissions of Chlorinated Solvents from
Aerosol Packagers (1988) 129
32 Estimated Methylene Chloride Emissions from Aerosol Packagers
in 1987 131
33 Emissions from Three Points at a Pesticide Facility, 1988 137
v
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LIST OF FIGURES
Figure Page
1 Locations of Plants Manufacturing Methylene Chloride ... 17
2 Process Flow Diagram for the Production of Methylene Chloride
and Co-products by the Direct Chlorination of Methane. . . 19
3 Process Flow Diagram for the Production of Methylene Chloride
and Co-Products by the Hydrochlorination of Methanol ... 21
4 Process Flow Diagram for the Production of Polycarbonate Resin
56
5 Process Flow Diagram for the Production of Triacetate Fibers 66
6 Schematic Flow Diagram of Polyurethane Flexible Foam
Production 76
7 Typical Synthetic Organic Pharmaceutical Chemical Process . 86
8 Pan Tablet Coating Process Solvent Recovery System .... 94
9 Wurster Process Solvent Recovery System 96
10 Open Top Vapor Cleaner 101
11 Cross-Rod Cleaner 103
12 Monorail In-Line Cleaner 105
13 Schematic Diagram of an In-Line Photoresist Stripping Machine06
14 Carburetor Cleaner 108
15 Batch Cleaner Idling Emission Sources 109
16 In-Line Cleaner Emission Sources 110
17 Typical Aerosol Spray System 125
18 Photographic Film Process with MC Emissions 139
19 Schematic Diagram of Volatile Organic Sampling Train (VOST) 146
20 Schematic Diagram of Trap Desorption/Analysis System . . 148
21 Integrated Bag Sampling Train 150
VI
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SECTION 1
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 at certain
concentrations. This awareness has led to attempts to identify
source/receptor relationships and to develop control programs to
regulate toxic 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 one, that compiles available information on
sources and emissions. Existing documents in the series are listed
below.
Substance
Aerylonitrile
Carbon Tetrachloride
Chloroform
Ethylene Bichloride
Formaldehyde (Revised)
Nickel
Chromium
Manganese
Phosgene
Epichlorohydrin
Vinylidene Chloride
Ethylene Oxide
Chlorobenzenes
Polychlorinated Biphenyls (PCBs)
Polycyclic Organic Matter (POM)
Benzene
Organic Liquid Storage Tanks
Coal and Oil Combustion Sources
Municipal Waste Combustors
Perchloroethylene and
1,3-Butadiene
Chromium (supplement)
Sewage Sludge
Styrene
EPA Publication Number
EPA-450/4-84-007a
EPA-450/4-84-007b
EPA-450/4-84-007C
EPA-450/4-84-007d
EPA-450/2-91-012
EPA-450/4-84-007f
EPA-450/4-84-007g
EPA-450/4-84-007h
EPA-450/4-84-007i
EPA-450/4-84-007J
EPA-450/4-84-007k
EPA-450/4-84-0071
EPA-450/4-84-007m
EPA-450/4-84-007n
EPA-450/4-84-007p
EPA-450/4-84-007q
EPA-450/4-88-004
EPA-450/2-89-001
EPA-450/2-89-006
EPA-450/2-90-013
EPA-450/2-89-021
EPA-450/2-89-002
EPA-450/2-90-009
EPA-450/4-91-029
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This document deals specifically with methylene chloride (MC),
also known as dichloromethane. The intended audience includes
Federal, State and local air pollution personnel and others who are
interested in locating potential emitters of MC and in making gross
estimates of MC air emissions.
Data on some potential sources of MC emissions are limited and
the configurations of many sources will differ from those described
here. Therefore, this document is best used as a primer to inform air
pollution personnel about (1) the types of sources that may emit MC,
(2) process variations and release points that may be expected within
these sources, and (3) available emissions information indicating the
potential for MC to be released into the air from each operation.
The reader is strongly cautioned against using the emissions
information contained in this document 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 MC 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.
In addition to the information presented in this document,
another potential source of MC emissions data is the Toxic Chemical
Release Inventory (TRI) form required by Section 313 of Title III of
the Superfund Amendments and Reauthorization Act of 1986 (SARA 313.J1
SARA 313 requires owners and operators of certain facilities that
manufacture, import, process, or otherwise use certain toxic chemicals
to annually report releases 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
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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). In
addition, for 1989 and subsequent years, only those facilities
manufacturing or processing in excess of 25,000 Ibs/yr (11,340 kg/yr)
of MC, or otherwise using in excess of 10,000 Ibs/yr (4,540 kg/yr) of
MC, were required to report MC emissions.2 Thus, facilities that emit
MC but fall below these thresholds may not be included in the
TRI database.
The reader is urged to obtain TRI data in addition to the
information provided in this document to locate potential emitters of
MC and to make preliminary estimates of air emissions from these
facilities. To obtain an exact assessment of air emissions from
processes at a specific facility, source tests or detailed material
balance calculations should be conducted, and detailed plant site
information should be compiled.
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REFERENCES FOR SECTION 1
1. Toxic Chemical Release Reporting: Community Right-To-Know,
52 FR 21152-21208, June 4, 1987.
2. Toxic Chemical Release Inventory Reporting Package for 1990,
EPA 560/4-91-001, U.S. Environmental Protection Agency,
January 1991, p. 9.
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SECTION 2
OVERVIEW OF DOCUMENT CONTENTS
This section outlines the nature, extent, and format of the
material presented in the remaining sections of this report.
Section 3 briefly summarizes the physical and chemical
characteristics of MC, and provides an overview of its production and
use. This background section may be useful in developing a general
perspective on the nature of MC and how it is manufactured and
consumed.
Sections 4 and 5 focus on major source categories that may
discharge MC air emissions. Section 4 discusses emissions from the
production of MC; Section 5 discusses emissions from the major uses of
MC.
Example process descriptions and flow diagrams, potential
emission points, and available emission factor estimates that show the
potential for MC emissions before and after controls are presented for
each major industrial source category described in Section 4 and 5.
Also included are the names of individual companies that either
produce or use MC, based primarily on information from trade
publications.
Section 6 summarizes available procedures for source sampling and
analysis of MC. Details are not prescribed nor is any EPA endorsement
given or implied to any of these procedures. At this time, EPA has
not generally evaluated these methods. Consequently, this document
merely provides an overview of applicable source sampling procedures,
citing references for those interested in conducting source tests.
This document does not contain any discussion of health or other
environmental effects of MC, nor does it include any discussion of
ambient air levels or ambient air monitoring techniques.
Comments on the contents or usefulness of this document are
welcome, as is any information on process descriptions, operating
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practices, control measures, and emissions that would enable EPA to
improve its contents. All comments should be sent to:
Chief, Emission Factor and Methodologies Section
Emission Inventory Branch (MD-14)
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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SECTION 3
BACKGROUND
NATURE OF POLLUTANT
Methylene chloride (Chemical Abstracts Registry Number 75-09-2),
a saturated aliphatic halogenated hydrocarbon, is a clear, colorless,
volatile liquid with an odor similar to ether. Methylene chloride is
a chemical used in many applications because of its high solvency, low
corrosiveness to many metals, and lack of flash or fire point.1 It was
introduced as a replacement for more flammable solvents over 60 years
ago because of its extensive oil and fat solubility, and low
flammability potential.
Methylene chloride's molecular structure is represented as:
H
Cl C Cl
H
Table 1 shows the chemical and physical properties of MC.2"4
Methylene chloride is released to the atmosphere during its
production and use. The EPA has indicated that MC may be exempted
from regulation as a volatile organic compound (VOC) under state
regulations implementing the national ambient air quality standard for
ozone because it is not considered to appreciably contribute to ozone
formation; however, MC is on the list of 189 hazardous air pollutants
(HAP's) to be regulated under Section 112 of the Clean Air Act
(Title III). Methylene chloride waste solvent is considered a
hazardous waste under the Resource Conservation and Recovery Act
(RCRA) because it poses a human health threat as a probable human
carcinogen and neurotoxin. The reportable quantity for releases (any
spilling, leaking, pumping, pouring, emitting, emptying, discharging,
injecting, escaping, leaching, dumping, or disposing into the
environment, excluding those releases that result in exposure to
persons solely in the workplace and emissions from the engine exhaust
of a motor vehicle, rolling stock, aircraft, vessel or pipeline
pumping station) under the Comprehensive Environmental Response,
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TABLE 1. CHEMICAL AND PHYSICAL PROPERTIES OF METHYLENE CHLORIDE
Synonyms
Chemical Abstracts Registry Number
Molecular formula
Molecular weight
Ambient state
Odor threshold
Boiling point at 101.3 kPa (760mmHg)
Freezing point
Density, at 20°C kg/m3
Specific gravity, at 20°C
Vapor density (air = 1.02)
Vapor Pressure:
kPa at 0°C
kPa at 20°C
kPa at 30°C
Diffusivity in air, m /s
Refractive index at 20°C
Coefficient of cubical expansion (20-35°C)
Viscosity at 20°C mPa x s (=cP)
Surface tension:
N/m (=dyn/cm) at 20°C
Heat of combustion, MJ/kg
Heat of vaporization:
at 20°C, KJ/kg (Btu/lb)
at 20°C, Kcal/kg
Heat capacity:
at 25° C, J/mol
at 25°C, cal, mol
Solubility
Dichloromethane (DCM), methylene dichloride, methylene
bichloride, methane dichloride
75-09-2
CH2C12
84 .9
Clear, colorless, volatile liquid
Between 100 and 300 ppm ethereal odor
39.8°C
-96 .7°C
1315 .7
1 .320
2 .93
19.6
46 .5
68 .1
9 X 10~5
1 .4244
.0014
.43
.02812
7.1175
329.23 (141.7)
78 .69
Flash point (ASTM) D1310-67
Flammable (explosive) limits
at 25°C, vol% in air
Auto-ignition temperature
Electrical properties at 24°
Dielectric strength, V/cm (V/100 mils)
Specific resistivity at 24°, fi • cm
54 .09
12 .93
Soluble with other grades of chlorinated solvents, diethyl
ether, ethanol, ethyl alcohol, phenols, aldehydes, ketones,
glacial acetic acid, triethyl phosphate, acetoacetic ester,
and water (13.2 g/kg at 20°C).
None, however, as little as 10 vol% acetone or methyl
alcohol can produce one.
14-25
640°C
94.488 (24.00)
1.81 X 10
i n
Source: References 2, 3, and 4.
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Compensation, and Liability Act (CERCLA, or Superfund), is
1,000 pounds (454 kg).
In 1989, the Food and Drug Administration banned the use of MC in
cosmetic products. Since 1990, the Consumer Product Safety Commission
has required manufacturers, importers, packagers, and private labelers
of consumer products containing 1 percent or more MC to report such
information on product labels and in product marketing.
In November 1991, the Occupational Safety and Health
Administration published a proposal to amend its existing regulation
for employee exposure to MC.5 The proposed standard, which would
impact a number of industries, lowers the permissible exposure limit
from 500 ppm MC to 25 ppm.
OVERVIEW OF PRODUCTION AND USE
Methylene chloride is produced in the United States by three
companies at five plants with an estimated combined production
capacity of 250 Mg (551 million pounds) .6 Total 1991 production of MC
was 182 Mg (400 million pounds), of which an estimated 33 percent
(60 Mg or 132 million pounds) was exported.6 In 1991, use of MC in the
United States was approximately 126 Mg (277 million pounds) of which 2
percent (3 Mg, or 7 million pounds) was imported.6
Methylene chloride demand in the United States has declined
steadily in recent years with an estimated 15 percent decline in 1991.6
This decline can be attributed to solvent recycling, environmental and
occupational health concerns, and a slow economy.
Methylene chloride end uses include:
• as an active ingredient in solvent-based nonflammable paint
removers/strippers;
• in the manufacture of polycarbonate resins;
• in the production of cellulose triacetate;
• as an auxiliary foam blowing and mold-releasing agent;
• as a carrier for pharmaceutical tablet coatings;
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• as a solvent in vapor and nonvapor metal cleaning processes;
• as a solvent in aerosols;
• for photoresist stripping in electronic circuit board
manufacture;
• as an inert ingredient in pesticides; and
• as an extractant in the recovery of oleoresins, oils, fats,
and waxes.6'7
Table 2 shows the estimated U.S. consumption by end use for 1991.s
Methylene chloride end use processes are discussed in detail in
Section 5.
Table 3 lists potential source categories of MC emissions by
their two-digit Standard Industrial Classification (SIC) code.8 These
source categories presented by SIC code represent MC use by a
particular industry. The processes using MC within these industries
are not reported in the TRI data used to generate Table 3. For
example, within the Chemicals and Allied Products SIC code (which
includes production of MC and other chemicals, plastics,
Pharmaceuticals, pesticides, and other products), MC may be used as an
ingredient in the product or as a solvent, paint remover, or metal
cleaner elsewhere in the plant.
10
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TABLE 2. ESTIMATED UNITED STATES METHYLENE CHLORIDE
CONSUMPTION BY END USE FOR 1991
[in Mg (Million Pounds)]
Paint Removal/Stripper 39,100 (86)
Plastics (polycarbonate resins, triacetate fiber) 20,000 (44)
Flexible Polyurethane Foam 17,700 (39)
Pharmaceuticals 13,600 (30)
Metal Cleaning/Degreasing 13,600 (30)
Aerosols 10,000 (32)
Electronics 5,000 (11)
Miscellaneous (pesticides, food processing, 6,400 (14)
and synthetic fibers)
Total 125,400
(276)
Source: Reference 6.
11
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TABLE 3. POTENTIAL SOURCE CATEGORIES OF METHYLENE CHLORIDE EMISSIONS
SICa
Code
28
30
37
34
36
35
33
32
38
39
25
22
26
27
51
31
29
20
23
24
73
00
50
49
97
87
46
08
75
02
96
47
42
45
Source
Description
Chemicals and Allied Products
Rubber and Miscellaneous Plastics
Products
Transportation Equipment
Fabricated Metal Products
Electric & Other Electronic Equipment
Industrial Machinery and Equipment
Primary Metal Industries
Stone, Clay, and Glass Products
Instruments and Related Products
Miscellaneous Manufacturing Industries
Furniture and Fixtures
Textile Mill Products
Paper and Allied Products
Printing and Publishing
Wholesale Trade Nondurable Goods
Leather and Leather Products
Petroleum and Coal Products
Food and Kindred Products
Apparel and Other Textile Products
Lumber and Wood Products
Business Services
Blank
Wholesale Trade Durable Goods
Electric, Gas, and Sanitary Services
National Security and Intl. Affairs
Engineering & Management Services
Pipelines, except Natural Gas
Forestry
Auto Repair, Services, and Parking
Agricultural Production Livestock
Administration of Economic Programs
Transportation Services
Trucking and Warehousing
Transportation by Air
TOTAL
Number of Plants
Reporting the Use of
MC
653
278
164
139
137
85
68
53
49
42
28
25
19
16
15
12
11
11
9
9
3
3
2
2
2
2
1
1
1
1
1
1
1
1
1,845
Source: Reference 8.
a SIC = Standard Industrial Classification
12
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REFERENCES FOR SECTION 3
Chemical Products Synopsis, "Methylene Chloride," Mannsville
Chemical Products Corporation, Asbury Park, NJ, December, 1990.
"IARC Monographs on the Evaluation of the Carcinogenic Risk of
Chemicals to Humans," International Agency for Research on
Cancer, World Health Organization, Lyon, France, October 1979,
pp. 449-450.
T. Anthony, "Methylene Chloride, Chlorocarbons and
Chlorohydrocarbons (CH2C12)," Encyclopedia of Chemical Technology,
Third Edition, John Wiley & Sons, Inc, New York, 1983, p. 687.
T. Anthony, "Methylene Chloride, Chlorocarbons and
Chlorohydrocarbons," Concise Encyclopedia of Chemical Technology,
John Wiley & Sons, Inc, New York, 1985, p. 262.
Occupational Safety and Health Administration Proposal for New
Methylene Chloride Standard, 56 FR 57036, November 7, 1991.
"Chemical Profile--Methylene Chloride," Chemical Marketing
Reporter, 241(9) :42, March 2, 1992.
White Paper -- Methylene Chloride, Halogenated Solvents Industry
Alliance, Washington, DC, February 1989.
Memorandum and attached computer file from E. Cotter, SYCOM,
Washington, DC, to C. Thornton, U.S. Environmental Protection
Agency, Research Triangle Park, NC, April 22, 1992.
13
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14
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SECTION 4
EMISSIONS FROM METHYLENE CHLORIDE PRODUCTION
As noted in Section 3, MC is produced in the United States by
three companies at five plants. These plants, and associated
locations, are presented in Table 4.1 Figure 1 illustrates plant
locations. Dow and Occidental Chemical both report methanol for use
as a raw material in their production of MC, and Vulcan Materials
Company reports 33 percent methane and 67 percent methanol for use as
a raw material in their production of MC.2
Methylene chloride is generally stored in outdoor tanks and is
distributed in bulk quantities by tank truck, railcar, barge, or 55-
gallon drums. Production equipment includes storage tanks, reactor
vessels, distillation columns, scrubbers, drying towers, pumps,
valves, conduits, and piping.
PROCESS DESCRIPTIONS
In the United States, MC is produced by two processes: (1)
direct chlorination of methane to produce methyl chloride, and (2)
hydrochlorination of methanol to produce methyl chloride. Methyl
chloride produced by both of these processes is chlorinated further by
chlorine to produce methylene chloride. The predominant production
process in the United States is the hydrochlorination of methanol.3
Methylene chloride production, regardless of the process method
employed, is a continuous production process that takes place in an
enclosed system.4 Both MC production processes are described in the
following paragraphs.
Direct Chlorination of Methane
The direct chlorination of methane yields MC by the direct
reaction of excess methane (natural gas) with chlorine at a high
temperature (340-370°C) and at a pressure slightly above one
atmosphere, producing methyl chloride, MC, chloroform, and carbon
tetrachloride as coproducts ,3'4
15
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TABLE 4. UNITED STATES METHYLENE CHLORIDE PRODUCTION
Production
Producer Location Process
Dow Chemical U.S.A. Freeport, Texas Hydrochlorination of
Methanol
Dow Chemical U.S.A. Plaquemine, Hydrochlorination of
Louisiana Methanol
Occidental Petroleum Belle, West Hydrochlorination of
Corporation Virginia Methanol
Vulcan Materials Geismar, Hydrochlorination of
Company Louisiana Methanol
Vulcan Material Company Wichita, Kansas Hydrochlorination of
Methanol and Chlorination
of Methane
Note: LCP Chemicals closed a 27 Mg (60 million-pound) production
capacity plant in Moundsville, West Virginia, in
August 1991.1
Source: References 1, 2 and 3.
16
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LEGEND OF PLANT NAMES AND LOCATIONS
1. Dow Chemical U.S.A., Fraaport, TX
2. Dow Chamteal U.SA, Plaquamina, LA
3. Occlo*ntal Patrolaum Corporation, Balla, VVV
4. Vulcan Materials Company, Gaiamar, LA
3. Vulcan Matariato Company, Wichita, KA
Sources: References 1 and 2
Figure 1. Locations of plants manufacturing Methylene Chloride.
17
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The process entails mixing methane with chlorine and then feeding
the mixture to a chlorination reactor where MC, methyl chloride,
chloroform, and carbon tetrachloride are formed. The co-products are
separated by distillation and methyl chloride is recycled back to the
chlorination reactor, where it can be controlled to yield mostly MC.
This chlorination process is illustrated by the following reactions.3'5
CH4 + C12 > CH3C1 + HC1
(methane) (chlorine) (methyl chloride) (hydrogen chloride)
CH3C1 + C12 > CH2C12 + HC1
(methyl chloride) (chlorine) (methylene chloride) (hydrogen chloride)
CH2C12 + C12 > CHC13 + HC1
(methylene chloride) (chlorine) (chloroform) (hydrogen chloride)
CHC13 + C12 > CC14 + HC1
(chloroform) (chlorine) (carbon tetrachloride) (hydrogen chloride)
A process flow diagram illustrating the direct chlorination of methane
to produce MC is presented in Figure 2.3
Hydrochlorination of Methanol
Hydrochlorination of methanol involves the vapor-phase reaction
of hydrogen chloride and methanol with the addition of a catalyst at
180-200°C to the hydrochlorination reactor, (maintained at 350°C)
which yields methyl chloride.5 The exit gases from the reactor pass
through a quench tower, scrubber, and drying tower prior to yielding
methyl chloride.5 Methyl chloride then undergoes further chlorination,
stripping, and distillation to yield MC and chloroform. These
chlorination processes are illustrated by the following reactions.3'5
CH3OH + HC1 catalyst „ CH3C + H2O
(methanol) (hydrogen chloride) vapor-phase (methyl chloride) (water)
CH3C1 + C12 > CH2C12 + HC1
(methyl chloride) (chlorine) (methylene chloride) (hydrogen chloride)
CH2C12 + C12 > CHC13 + HC1
(methylene chloride) (chlorine) (chloroform) (hydrogen chloride)
CHC13 + C12 > CC14 + HC1
(chloroform) (chlorine) (carbon tetrachloride) (hydrogen chloride)
18
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Recycled Methane
Methane
Chlorine
Spent
Caustic
Denotes Potential Location
of Emission Source
Source: Reference 3
Drying Agent
CH4 + HCI
s
!
\
A
Scrubber/
Absorber
System
Hot Water »
HCI
Absorber
w
Methyl
Chloride
NaOH
Y
HZS04
Spent Caustic Spent Acid
Methylene
Chloride
Storage
Heavy
Ends
Carbon
Tetrachloride
Figure 2. Process flow diagram for the production of Methylene Chloride and
co-products by the direct chlorination of methane.
-------
Catalysts that are often employed in this process include cuprous
chloride, activated charcoal, and zinc chloride.3 The
hydrochlorination of methanol process to produce MC is illustrated in
Figure 3.
EMISSION SOURCES AND CONTROLS
In 1985, producers of MC, in response to Section 114
questionnaires, provided estimates and sources of emissions from their
1983 MC production process. The largest sources of emissions reported
by all six plants operating at the time were equipment leaks, storage
tanks, and transfer emissions (i.e., loading MC into railroad tanks
and truck tanks, and drum filling). Other sources reported by all six
plants included process vents, equipment openings, relief devices, and
secondary emissions (e.g., wastewater treatment). Because production
equipment components, including storage tanks and loading facilities,
are often located outdoors, MC solvent losses due to leaks (i.e.,
from gaskets, pipe couplings, pumps, valves, and in-line sampling
ports) are often dispersed directly to the atmosphere.4
Equipment Leak Emissions
Equipment emissions result from leaking process equipment that
contains either liquid or gaseous MC. These emissions may occur
intermittently or continuously. The largest sources of equipment
leaks reported by MC production facilities in 1985 were from process
valves, flanges, pressure relief devices, and pump seals.3 Other
production process components that may leak include compressors, open-
ended lines, and sample connections.
Table 5 presents control techniques and efficiencies applicable
to equipment leak emissions.
Storage Tank Emissions
Methylene chloride storage tank emissions result from breathing
losses due to changes in barometric pressure and temperature, and
working losses due to volumetric changes in the tank from filling or
dispensing stored solvent. Outdoor tanks, because they are subjected
20
-------
K>
CataVst
Methanol
HCI
Denotes Potential Location
of Emission Source
Source: Reference 3
^
A
*k
Chlo'rination
Reactor
fs
Water
HCI
I
Y
Dilute Acid
Methyl Chloride
•s
1
u
CO
.. Caustic
Soda
H2S04 —
/s
en Is
c 9
E-5
Q»-
L j
Spent Caustic
Spent Acid
ii
ilorine
A
( \
if?
is*
vJ
jK
(\
g
^
o
Chloride
_. _. , . Storage
^ Chloroform a
Carbon Tetrachloride
and Heavy Ends
Figure 3. Process flow diagram for the production of Methylene Chloride and
co-products by the hydrochlorination of methanol.
-------
TABLE 5. CONTROL TECHNIQUES AND EFFICIENCIES APPLICABLE TO EQUIPMENT LEAK EMISSIONS
Equipment Component
(Emission Source)
Control Technique
Percent
Reduction
K>
Pump Seals
Packed and Mechanical
Double Mechanical9
Compressors
Flanges
Seal area enclosure vented to a control device (closed-vent system)
Monthly LDAR
Quarterly LDAR
Closed-vent system
Vent degassing reservoir to control device (closed-vent system)
Annual LDAR program
100
61
33
100
Valves
Gas
Liquid
Pressure Relief Devices
Gas
Liquid
Sample Connections
Open-ended Lines
Monthly LDAR
Quarterly LDAR
Monthly LDAR
Quarterly LDAR
Monthly LDAR (safety concerns)
Quarterly LDAR (safety concerns)
Rupture Disk w/closed-vent system
N/A
Closed-purge Sampling
Caps/plugs/flanges/secondary valves
73
64
59
44
50
44
100
b
100
100
Source: Reference 7.
aAssumes 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.
bNot established.
LDAR = Leak detection and repair
N/A = Not applicable
-------
to greater diurnal temperature variation, have a greater potential for
MC emission losses than indoor tanks.
Storage tank emissions are controlled through tank modifications
(i.e., by adding an internal floating roof to a fixed-roof tank), use
of a conservation vent, or by collecting and routing vapors from the
storage tank to a control device such as a condenser. A conservation
vent, which is a type of pressure- and vacuum-relief valve, is
commonly installed on fixed roof tanks to contain minor changes in
vapor volume. The use of these valves prevents the release of vapors
during times when there are only small pressure differentials
(e.g., +0.2 kPa). Emissions reduction achieved by the use of these
valves are dependent on the vapor pressure of the stored liquid.
Conversion of a fixed-roof tank to a floating roof could reduce
MC emissions by roughly 80-90 percent, depending on the tank design,
type of roof seals and fittings, temperature, throughput, number of
turnovers, and other factors.6 Condensers and other product recovery
or combustion control devices can be designed for 95 percent
efficiency.
Transfer Emissions
Transfer emissions from MC production processes occur from
loading MC into tank cars, trucks, or barges for transport. Fugitive
emissions during transfer can result through the hatches and other
openings of tank trucks and tank cars that are not vapor tight.
Loading losses occur by three mechanisms: displacement of vapors that
are transferred into the vehicle via the vapor balance system as the
previous product was unloaded; displacement of vapors formed in the
empty tank by evaporation of residual products from previous loads;
and vapor displacement and volatilization as a result of turbulence
and vapor/liquid contact during loading of the new product. Transfer
emissions may be controlled by vapor balancing, where MC vapors are
returned to the storage tanks and the use of submerged loading rather
than splash loading. In splash loading, the fill pipe dispensing the
chemical is lowered only partway into the transport vessel
(i.e., barge, tank car, or tank truck). Significant turbulence and
vapor/liquid contact occur during splash loading, potentially
resulting in a high degree of vapor generation and loss, submerged
loading (submerged fill pipe method and bottom-loading method)
23
-------
involves loading a fill pipe opening that is below the liquid surface
level for most of the loading operation; therefore, minimizing liquid
turbulence and reducing the vapor generation that occurs with splash
loading. The reader is referred to EPA Publication No. AP-42,
Section 4.4.2 for the estimation of loading losses. Alternatively,
transfer emissions may be vented to a product recovery device or a
combustion device. A product recovery device uses refrigeration,
absorption, adsorption and/or compression. The recovered product is
piped back to storage. Combustion is generally through thermal
oxidation, without any recovery. Both product recovery and combustion
methods can be designed to achieve over 95 percent emission reduction.
Process Vents
Production processes may emit MC through process vents from the
reactors and distillation columns. These process vent streams are
typically routed through product recovery devices (e.g., scrubbers,
condensers) as part of the production process, so much of the MC is
recovered before the vent stream is emitted to the atmosphere.
No emission factors were found for process vent emissions, which
would be highly site-specific. Emission estimates supplied by MC
production plants for 1983 are included in the "Emission Estimates"
part of this section. In order to further reduce emissions, vent
streams could be routed to a combustion device after the final
recovery device. Combustion devices can reduce VOC emissions by about
98 percent.8 No data specific to MC reduction efficiencies by
combustion were available at the time this study was conducted.
Secondary Emissions
Secondary emissions from MC production occur from on-site and
off-site treatment and disposal of process-generated wastewater,
liquid waste, or solid waste. Waste streams can be generated from any
of the operations shown in Figures 2 and 3.
There is a potential for air emissions when MC-containing
wastewater comes in contact with the ambient air as the wastewater
passes through collection and treatment units. Factors that affect
24
-------
the magnitude of emissions include the MC concentration, wastewater
temperature, and collection and treatment system design.
Several types of controls apply to MC emissions from waste and
wastewater, including:
• Covers or enclosures such as fixed roofs, floating roofs,
and floating membranes;
• Covers or enclosures with closed-vent systems and control
devices such as carbon adsorbers or vapor incinerators;
• Treatment processes to remove MC;
• Waste incineration; and
• Process modifications to reduce the amount of MC wasted.
Efficiencies achievable by some of these types of controls are shown
in Table 6.9'10
Controls and estimated control efficiencies at facilities
producing MC in 1985, based on information reported by six facilities,
are presented in Table 7.3
EMISSION ESTIMATES
Emissions from MC production processes are determined by site-
specific sources; therefore, parameters for estimating emissions may
vary from site to site. Whenever possible, emissions derivations
should be specific to the facility.
Storage tank emissions for fixed-roof storage tanks and floating
roof storage tanks for a particular site can be estimated by
incorporating site-specific parameters using the EPA Publication No.
AP-42 emission factors for storage of organic liquids.11 Site-specific
parameters include, but are not limited to, tank diameter, tank
capacity, average diurnal temperature change, turnover factor, average
vapor space height, and plant factors. Most storage tanks reported by
MC production facilities in 1985 were fixed-roof storage tanks, with
only one report of a floating roof storage tank.3 The equations
25
-------
TABLE 6. WASTE AND WASTEWATER EMISSION CONTROL
TECHNIQUES AND EFFICIENCIES
Type of Control
Control Technique
Efficienc
y (%)
Cover on storage or treatment
tank
Cover on surface impoundment
Cover with closed-vent system
routed to control device
Treatment
Waste incineration
Fixed roof
External floating roof
Internal floating roof
Floating membrane
Carbon adsorber
Condenser
Thermal and catalytic
vapor incinerators
Flare
Steam stripping
Thin film evaporation
86-99a
93-97a
93-97a
85
95
95
99
99
99.99
Source: References 9 and 10.
a Dependent on concentration of MC in waste stream.
26
-------
TABLE 7. 1983 REPORTED CONTROLS AND CONTROL EFFICIENCIES FROM FACILITIES PRODUCING METHYLENE
CHLORIDE
Reported Control
Company/Location Type of Emission/Source 1983 Controls Efficiency
Diamond Shamrock Process
Belle, WV • Regeneration Vent None
• Vent Recovery System 1 Condenser
• Vent Recovery System 2 Condenser
Equipment Leaks
Storage
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
• Fixed-Roof
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Tank
Equipment Opening
None
Conservat ion
Water Cooled
Conservation
Water Cooled
Conservation
Water Cooled
Conservat ion
Water Cooled
None
None
Conservation
Water Cooled
Conservation
Water Cooled
None
None
None
None
None
None
Conservation
Water Cooled
Refrigerator
Conservat ion
Water-Cooled
None
Vent
Condenser
Vent
Condenser
Vent
Condenser
Vent
Condenser
Vent
Condenser
Vent
Condenser
Vent
Condenser
Condenser
Vent
Condenser
0
68
26
0
62
86
86
86
0
0
41
41
0
0
0
0
0
0
90
62
0
.5
.7
.4
.7
.7
.7
.9
.9
.7
.4
-------
TABLE 7. (CONTINUED)
Company/Locat ion
Type of Emission/Source
1983 Controls
Reported Control
Efficiency
tank trucks None
None
Dow Chemical
Freeport, Texas
Transfer
• Tank cars,
• Barges
Secondary
• Wastewater Treatment
Influent
• Solid Waste Drumming
• Sludge disposal
Relief Devices
Equipment Leaks
Steam Stripping/
Carbon Adsorption
Landfill
Off-site Treatment
N/A
None
0
0
N/R
N/R
N/R
Dow Chemical
Plaquemine, LA
Storage
• #
Equipment Opening
Handling
• Tank trucks, tank
cars, ships, barges
• Drums
Secondary
• Wastewater rain and
washdown
• Spent filter elements
Equipment Leaks
#
None
None
Flume vacuum system
Nonbiological treatment
Material and Energy
Recovery Unit
None
#
0
0
N/R
0
N/R
0
-------
TABLE 7. (CONTINUED)
Company/Locat ion
Type of Emission/Source
1983 Controls
Reported Control
Efficiency
LCP Chemicals
Moundsville, WV
Storage
• Fixed-Roof Tank
• Fixed-Roof Tank
• Fixed-Roof Tank
• Fixed-Roof Tank
• Fixed-Roof Tank
• Contact Internal
Floating-Roof
Equipment Opening
Handling
• Tank truck, tank car,
barges
Secondary
• Not identified
Relief Devices
Process
• Purge Condenser
• Recovery Tank
Equipment Leaks
Storage
Fixed Roof Tank
Fixed Roof Tank
Fixed Roof Tank
Fixed Roof Tank
Fixed Roof Tank
Fixed Roof Tank
Fixed Roof Tank
Handling
• Rail cars, truck
None
None
None
None
None
N/A
None
None
None
N/A
Compression and
Condensat ion
None
None
None
None
None
None
None
None
None
None
0
0
0
0
0
N/R
0
N/R
0
0
0
0
0
0
0
-------
TABLE 7. (CONTINUED)
Company/Locat ion
Type of Emission/Source
1983 Controls
Reported Control
Efficiency
Secondary
• Not Identified
• Not Identified
• Not Identified
Distillation and
Recovery
Neutralization and
Carbon Adsorption
Off-site
N/R
N/R
N/R
Vulcan Chemicals
Geismar, LA
Vulcan Chemicals3
Wichita, KS
Relief Devices
Process Vents
Equipment Leaks
Handling
Secondary
Relief Devices
Process Vent
Equipment Leaks
Storage
Equipment Opening
Handling
N/A
#
#
#
#
#
#
#
#
#
#
#
#
#
#
#
#
#
#
#
#
Source:Reference 3
* This information is considered by the company to be confidential.
a Company reported greater than 98 percent control, but 98 percent was used in the absence of
supporting test data.
N/A = Not Applicable
N/R = Not Reported
-------
for the estimation of storage emissions for a fixed-roof storage tank
using AP-42 methodology are presented in Appendix A.
The AP-42 section for evaporative losses from organic liquid
storage tanks was available in the October 1992 update to AP-42 known
as Supplement E. The update addresses changes that have occurred to
the emissions estimation equations for fixed and floating roof storage
tanks. A computer model called "TANKS," which incorporates the
equation changes and calculates emissions, has also been developed as
an aid in performing the extensive and detailed calculations required
to estimate emissions. The model contains look-up tables of default
values for equation variables when site-specific inputs are not known.
It can address situations of both single component liquids or mixtures
of compounds within a tank. The model can be obtained from EPA and
was made available to the public in September 1992 through the Office
of Air Quality Planning and Standards' (OAQPS') Technology Transfer
Network (TTN) Clearinghouse for Inventories/Emission Factors (CHIEF)
Bulletin Board. The TTN is operated by the Technical Support Division
of OAQPS in Research Triangle Park, North Carolina.
As with storage tank emissions, transfer emissions estimation
using EPA Publication No. AP-42 factors requires site-specific
handling inputs (i.e., dome loading, splash-fill loading, submerged
fillpipe, etc.).
Emission estimates for equipment leaks can be calculated in any
one of the five ways presented in the EPA publication "Protocols for
Generating Unit Specific Emissions Estimates" (the "Protocols"
document) .12 The five methods differ in complexity, with the more
complex methods yielding more reliable emission estimates.
The simplest method requires that the number of each component
type, the MC content of the stream, and the time that the component is
in service be known. These values are multiplied by the EPA's average
emission factors for the Synthetic Organic Chemical Manufacturing
Industries (SOCMI). The SOCMI factors are presented in Table 8. This
method is thought to overestimate actual equipment leak emissions;
therefore, it should be employed only when other data are not
available. Using this method, estimated emissions for each component
are calculated by the following equation.12
31
-------
TABLE 8. AVERAGE EMISSION FACTORS FOR EQUIPMENT LEAK EMISSIONS
Equipment
Service
Emission Factor
kg/hr/source
(Ib/hr/source)
Valve
Pump Seals
Compressor Seals
Pressure Relief Seals
Flanges
Open-Ended Lines
Sampling Connections
Gas
Light Liquid
Heavy Liquid
Light Liquid
Heavy Liquid
Gas/Vapor
Gas/Vapor
All
All
All
0.0056 (0.012)
0.0071 (0.016)
0.00023 (0.00051)
0.0494 (0.109)
0.0214 (0.472)
0.228 (0.503)
0.104 (0.229)
0.00083 (0.0018)
0.0017 (0.0037)
0.0150 (0.033)
Reference 13.
32
-------
Emissions Number of Percent Component- Number of Hour
from = Equipment • Weight of • Specific • per year MC
Component Components MC in Stream Emission Factor Component in Ser1
An example using this methodology is presented in Appendix A.
As noted, more accurate equipment leak emission estimates can be
obtained by one of the more complex estimation methods. Emission
measurement is required in varying degrees for the other four methods.
These methods are discussed briefly in the following text. For
further calculation details, the reader is referred to the "Protocols"
document.
The second method, the leak/no leak approach, is based on the
determination of the number of leaking and non-leaking components.
These values are multiplied by two different sets of EPA-derived
emission factors. The third method divides measurement data results
into three ranges; (1) 0-1,000 ppmv, (2) 1,001-10,000 ppmv, and (3)
greater than 10,000 ppmv. The number of each component within each
range is then multiplied by the component-specific emission factor
delineated by the EPA for that range. The fourth procedure uses
measurement data along with correlation equations derived by the EPA
in earlier work. The fifth method allows the facility to develop its
own correlation equations by using more rigorous testing, bagging and
analysis of equipment leaks to determine mass emission rates.12
The current "Protocols" document was published in 1988. It is
currently under revision. The reader is encouraged to refer to the
latest version when estimating emissions from equipment leaks.
An emission factor derived for the entire MC production process
is presented in Table 9. This factor was derived from 1983 aggregate
emission production totals for MC producers with 1983 controls. Site-
specific parameters will vary and it is recommended that current
site-specific emission factors be used. Also included in Table 9 are
equipment leak, storage, and inert gas purge vent product recovery
condenser emission factors for both methane chlorination and methyl
chloride chlorination MC production processes.14
33
-------
TABLE 9. EMISSION FACTORS FOR METHYLENE CHLORIDE PRODUCTION
Process
Source
Emission Factor
[g/kg MC produced (Ib/ton MC
produced)]
Methane
Chlorinat ion
Methane
Chlorinat ion
Methyl Chloride
Chlorinat ion
Inert gas
purge vent
product
recovery
condenser
Storage
Inert gas
purge vent
product
recovery
condenser
Methyl Chloride Storage
Chlorinat ion
Methylene
Chloride
Production
Wastewater
Treatment
Entire process
Publicly owned
treatment
works
0.14 (0.28!
1.02 (2.04)
0.03 (0.052)
2.46 (4.92!
3.00 (6.00;
520 g/kg MC influent
;i040 Ib/ton MC influent)
NOTE:
These emission factors were obtained from the XATEF data
base,-14 no information was supplied from the data base on
the number of tests or facilities used to derive the
factors. It is known, however, that the factor derived for
MC production (entire process) was from the six plants in
operation in 1984.3 It is suggested that facility-specific
information be used with the AP-42 and "Protocol" documents
referenced in the text to produce more accurate site-
specific emission estimates.
Source: Reference 14
34
-------
One emission factor that can be used to estimate MC emissions
based on MC influent to a publicly owned treatment works facility was
found in the literature and is presented in Table 9.14 Emissions of MC
from wastewater can be more accurately estimated using site-specific
data with the methodology presented in the EPA Control Technology
Center (CTC) document, "Industrial Wastewater Volatile Organic
Compound Emissions -- Background Information for BACT/LAER
Determinations . "10
35
-------
REFERENCES FOR SECTION 4
1. "Chemical Proflie--Methylene Chloride," Chemical Marketing
Reporter, 241(9):42, March 2, 1992.
2. "Methylene Chloride," 1991 Directory of Chemical Producers,
SRI International, Menlo Park, United States of America,
January 1991. p. 794.
3. Survey of Methylene Chloride Emission Sources, EPA-450/3-85-015,
U.S. Environmental Protection Agency. Research Triangle Park,
NC, June 1985.
4 . Occupational Safety and Health Administration Proposal for New
Methylene Chloride Standard, 56 FR 57044, 57054,
November 7, 1991.
5. "Selected Processes," Appendix III, EPA-450/3-80-028C,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
December 1980.
6. Julie Anne Probert, "Conversion of a Fixed-Roof Tank to a
Floating Roof Tank - MC Reduction," Calculation to File, Radian
Corporation, Research Triangle Park, NC, June 17, 1992.
7. Emission Factors for Equipment Leaks of VOC and HAP, EPA-450/3-
86-002, U.S. Environmental Protection Agency, Research Triangle
Park, NC, January 1986.
8. "Thermal Incinerator Performance for NSPS." Memorandum from
D. Mascone, Radian Corporation, Research Triangle Park, NC, to J.
Farmer, U.S. Environmental Protection Agency. June 11, 1980.
9. National Emission Standards for Hazardous Air Pollutants; Benzene
Emissions from Chemical Manufacturing Process Vents, Industrial
Solvent Use, Benzene Waste Operations, Benzene Transfer
Operations, and Gasoline Marketing System, Proposed Rule. 54 FR
38083. September 14, 1989.
10 . Industrial Wastewater Volatile Organic Compound Emissions --
Background Information for BACT/LAER Determinations, EPA-450/3-
90-004. Research Triangle Park, NC, January 1990.
11. "4.3 Storage of Organic Liquids," Compilation of Air Pollutant
Emission Factors: Volume I, Stationary Point and Area Sources,
Fourth Edition, AP-42, U.S. Environmental Protection Agency,
Research Triangle Park, NC, September 1985.
12 . Protocols for Generating Unit-Specific Emission Estimates for
Equipment Leaks of VOC and HAP, EPA-450/3-88-010,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
October 1988.
13 . Fugitive Emission Sources of Organic Compounds -- Additional
Information on Emissions, Emission reductions, and Costs, EPA-
450/3-82-010, U.S. Environmental Protection Agency, Research
Triangle Park, NC, 1982.
14. "Crosswalk/Air Toxic Emission Factor Data Base Management System
(XATEF), Version 1.2," Diskette, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1991.
36
-------
SECTION 5
EMISSIONS FROM USES OF METHYLENE CHLORIDE
The major industrial uses of MC include the production of paint
strippers (removers) (31 percent of total MC production); plastics
(16 percent); polyurethane foam (14 percent); Pharmaceuticals
(11 percent); degreasing operations (11 percent); aerosol production
(8 percent); and photoresist stripping (4 percent). The remaining
5 percent is consumed by various miscellaneous industries such as
pesticide production and photographic film processing.
This section presents the process descriptions, emission sources,
and emission controls and control efficiencies for the above
industrial use categories. When known, emissions estimates and
emissions factors or estimation methodologies are provided.
PAINT STRIPPER INDUSTRY
The formulation and use of paint strippers is discussed here.
Because little information is available on emissions of MC from
formulation and use of paints and coatings, the use of MC for this
purpose is discussed with other miscellaneous industrial uses of MC at
the end of this section.
A paint stripper is defined as a liquid, liquefiable, or mastic
composition whose primary function is to penetrate, blister, and
remove paint.1 A list of 113 U.S. facilities that formulate paint
strippers was identified by the U.S. Environmental Protection Agency
in 1987.2 Appendix B includes the names and locations of these
facilities. Responses to EPA Section 114 questionnaires pertaining to
MC and several other chlorinated organic emission sources with and
without emission controls in the paint stripping industry were
collected. These include twelve paint stripper formulator facilities,
six aircraft maintenance facilities, six military facilities, two
automobile producers, and one furniture repair facility.2'3 The
specific facilities are listed in the tables provided with this
section.
Separate estimates of MC used in the paint stripping industry
range from 61,600 Mg and 74,000 Mg annually.4 The use of paint
37
-------
strippers is divided into six major sectors: (1) aircraft
maintenance, (2) automobile applications, (3) industrial applications,
(4) military applications, (5) furniture manufacture, and
(6) household use. An estimate of the MC used by each sector is
presented in Table 10. Paint strippers for industrial use typically
contain 70-90 percent MC by weight; household paint stripping products
typically contain 60-80 percent.5
Methylene chloride has many properties that make it a highly
effective active ingredient. It easily penetrates, blisters, and
lifts paints from many substrates. It is also high in solvency, low
in flammability, and is not corrosive or damaging to metal or wood
surfaces.4 All of these properties, plus MC's relatively low price,
have prevented the substitution of other solvents in significant
quantities. The decrease in the amount of MC used in paint stripping
has been slow, but changes in OSHA regulations may increase the
incentive for development and use of substitutes.
For any operation, emissions are released from two types of
sources at a facility--building openings and process vents. Building
openings include general ventilation, doorways, windows, and other
fugitive loss points. Process vents include emissions related to a
specific process function, which do not enter the in-plant air, but
are emitted directly to the atmosphere through a pipe or duct. An
exhaust stack from an automotive refinishing spray booth is an example
of a process vent.
Process Descriptions
This section discusses paint stripper formulation processes and
their use in stripping operations.
Formulat ion--
Methylene chloride is generally supplied to paint stripping
facilities by a contracted chemical supplier. It is usually delivered
by tank car; however some smaller facilities may buy MC in 55-gallon
drums. Most facilities store MC in large, outdoor, fixed-roof tanks.
38
-------
TABLE 10. METHYLENE CHLORIDE CONSUMPTION IN 1987 BY PAINT STRIPPER
SECTOR
Methylene Chloride Used3
Sector (Mg/yr)
Automotive 15,400
Military Maintenance 14,500
Household 13,200
Other Industrial 10,100
Aircraft13 5,900
Commercial Furniture0 4,400
TOTAL 63,500
Source: Reference 3.
a Values shown represent the total MC present in the annual paint
stripper use
by each sector.
b Aircraft facilities include all maintenance and manufacturing
operations,
but do not include military aircraft.
c Commercial furniture includes all paint stripping removal operations
performed with office or residential furniture that are not
typically
performed by consumers.
39
-------
The paint stripper formulation process occurs in mixing tanks
ranging from several hundred to several thousand gallons in volume.
Mixing tanks are normally top-filled to three-quarters capacity. The
MC may be pumped directly from a storage tank or poured into the batch
directly from a 55-gallon drum. After the addition of an activator, a
corrosive inhibitor, an evaporation retarder, and a thickener, the
resulting product batch is heated to approximately 32°C and mixed for
several hours. After mixing, the paint stripper is pumped to an
automatic or manually operated filling machine. The product then
typically flows through a nozzle inserted through a bung hole on
the top of each container. This process can vary from two to ten
hours, depending on the size of the product batch.2
Stripping Operations--
Most automobile plants use MC-based paint strippers to clean
paint spray booths. In this process, the stripper is typically
sprayed onto the interior surfaces of the spray booth, allowed to
penetrate until the paint blisters, and then removed with a water
wash. In addition, many automotive plants use dip tanks to strip
paint from automobile parts or assembly equipment. Details of the
dipping process vary from plant to plant.
The other major use of MC in industrial plants is to remove paint
from floors. For this process, workers manually apply stripper and
remove paint by mopping and scraping. Some plants also use paint
strippers to purge paint lines. This stripping occurs in an
essentially closed system. Stripper is pumped into the lines, allowed
to stand, and pumped out when the lines are purged. The used stripper
is recovered for reuse, treatment, or disposal.3
Methylene chloride-based paint strippers are used to remove paint
overspray and clean defective paint jobs in general assembly line
operations used to manufacture durable goods.3 These processes are
similar to those used at automobile assembly plants in that the
cleaning is done manually in open processes.3 Some facilities also use
MC to clean conveyor hooks.5
In commercial aircraft repainting, MC-based paint removers are
sprayed onto the aircraft or part surface as a fine mist and allowed
to blister the paint. The paint is then washed off with non-metallic
40
-------
scrapers and is finally washed with water or a solvent rinse.5
Eighty percent of the MC used in this process evaporates and is
emitted through building openings. The remaining MC is collected as
runoff from the spraying procedure. This process occurs in large
general maintenance aircraft hangars.3
Military paint stripping processes are a combination of aircraft
and automobile processes. Most of the data associated with these
categories are related to aircraft maintenance operations.
In commercial furniture refinishing, paint or varnish is removed
by one of four methods. The most common method is by the use of a dip
tank. This process is completed by dipping the furniture into an open
tank of stripper for a designated time or until the paint blisters.
Afterwards, the paint is scraped off manually. This process may be
repeated several times if the paint is difficult to dry. A second
method is the flow-over system. This system automatically pumps
stripping solution to a brush that mechanically sweeps the furniture.
Excess stripper is recycled back into the system. Once blistering
occurs, the paint is manually scraped off. The spent solution is
either recycled, disposed of as hazardous waste, or left on site to
evaporate.5 The third method uses a combination of the dip tank and
flow-over system in series. The fourth method is simply manual
application and removal.5
Most paint stripper consumed by the household sector is used to
strip furniture.5 Consumers who strip furniture themselves typically
apply stripper with a brush and remove the paint with a scraper.
Insufficient information is available, however, to characterize the
emissions of MC from this process.3
Emissions
Emissions data are available for paint stripping formulators and
for some of the processes that use MC-based paint strippers. However,
data for all the end-uses are not available. Some of the end-use
data, such as those for aircraft and automotive facilities, are
included together because their processes and emission releases are
similar. Other end-use categories for which emissions data are well
established are presented individually.
41
-------
Paint Stripper Formulators--
Sources of MC emissions from paint stripper formulation include
storage, handling, equipment leaks, and secondary sources. Storage
tank emissions are the result of breathing losses and working losses.
Breathing losses are mainly caused by diurnal changes in temperature,
which can cause expansion and contractions of the tank. Working
losses are caused by filling or dispensing of the stored solvent,
which in turn forces MC vapors out of the void space of the tank.
Emissions from storage tanks are released either indoors or outdoors
depending on the tank location. Indoor storage tanks are assumed to
have negligible breathing-loss emissions because indoor diurnal
temperature changes are expected to be minimal. If pressurized tanks
are used to store solvents under pressures greater than atmospheric,
they do not have significant emissions.2
Handling emissions are the result of mixing tank operations and
product container filling. Current data suggest that the major source
of handling emissions are from the mixing operations. These emissions
may be released through general building openings or process vents
associated with mixing. In facilities that do not have process vents
for the mixing stage of production, all associated emissions would be
manifested as fugitive releases from building openings.
Emissions from process equipment components occur when the liquid
or gas process streams leak from the equipment. Process equipment
components upstream from the mixing tank typically contain solvent at
all times, and equipment leak emissions associated with them are also
continuous. The process equipment downstream from the mixing tank is
cleaned and drained after each product batch. These emissions only
occur during operating hours.
Secondary emissions include MC release associated with the
disposal of wastewater, solid waste, liquid waste, and accidental
spills.
Emission controls that may be incorporated in the storage tank
and mixing area include MC transfer controls (e.g., dome lead, splash-
fill, submerged fill-pipe), refrigerated condensers in storage tank
areas, and venting combined with carbon adsorbers. A chilling coil
with the capacity to lower the MC temperature from 25°F to -7°F at a
42
-------
rate of 220 g/s (approximately 30,000 Btu/hr), will lower the vapor
pressure of MC by more than 75 percent.2 Equipment leaks can be
controlled using a regularly scheduled leak detection and repair
(LDAR) program. Leak detection can be accomplished visually or using
a portable VOC analyzer to "sniff" around equipment components.
As discussed in Section 4, MC emissions from wastewater and
wastes can be controlled by treating to reduce MC, and prior to
treatment, by using covers and enclosures, either alone to suppress
emissions, or with a closed vent system that captures emissions and
routes them to a control device. Treatment techniques applicable to
MC-containing wastes and wastewaters include steam stripping, thin
film evaporation, and incineration.
Table 11 shows the results of emission control techniques as they
apply to specific formulation process components. This table includes
controls examined for a previous project, and therefore does not
include all the controls discussed above. Emission controls have been
the most effective on the two highest sources of emissions, storage
and mixing. Refrigerated condensers or carbon adsorbers applied to
these sources have been estimated to have an emission reduction
efficiency of 95 percent. As discussed in Section 4, internal
floating roofs applied to MC storage tanks can reduce emissions by
80 to 90 percent relative to fixed-roof tanks.
Emission estimates for paint stripper formulators were estimated
from the responses of 12 facilities to an EPA Section 114
questionnaire during a 1987 EPA project. The emissions estimates were
developed from data on the annual consumption of MC and questionnaire
information on the emission points associated with the formulation
process. Emissions were categorized into storage emissions, handling
emissions, and equipment leaks. The estimates developed for the 12
facilities responding to the questionnaire were used to represent the
other 101 facilities that EPA had identified. To estimate storage
tank emissions for the facilities that were not sent questionnaires,
outdoor fixed roof storage tanks were used to calculate the emission
factors used to estimate emissions from "typical" facilities because
most storage tanks are outdoors.2
43
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TABLE 11. CONTROL TECHNIQUES FOR EMISSIONS OF CHLORINATED SOLVENTS FROM PAINT STRIPPER FORMULATORS
Emission Source
Additional Controls
Emission Reduction Efficiency
Storage Tank
Mixing Tanks (Handling)
Equipment Leaksd
Pump Seals (packaged and
mechanical)
Flanges
Valves (liquid)
Valves (gas)
Sample Connections
Open-Ended Lines
Secondary Sources
Refrigerated condenser
Carbon adsorption13
Refrigerated condenser13
Monthly LDARe
None analyzed
Monthly LDAR
Monthly LDAR
Closed-purge sampling
Caps on open ends
Covers, enclosures,
treatment, incineration
95a
95 =
95a
61f
59f
73f
100f
100f
85-99.99
a Control Technologies for Hazardous Air Pollutants. EPA-625/6-86-014. U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina, September, 1987. p. 24.
b Control option also includes covering the mixing tank and installing ductwork from the mixing tank to
the adsorber or condenser to recover chlorinated solvent emissions.
c May, P. and G. Bockol, Memorandum: Assessment of Carbon Adsorbers for Control of Hazardous Air
Pollutants. Prepared by Radian Corporation for L. Evans of the U.S. Environmental Protection Agency,
December 1, 1986.
d Reference 10.
e "LDAR" means leak detection and repair.
f Percent reduction in VOC emissions based on the emission factors shown in Table A-l of Appendix A.
Methylene chloride emissions are assumed to be reduced by the same percent as total VOC emissions.
-------
These estimates were made by making many assumptions, however.
To obtain reliable emissions estimates for an individual site would
require additional site-specific information. As discussed in Section
4 for MC producers, site-specific emission estimates can be developed
using the AP-42 methodologies for storage tanks, the "Protocols"
methodologies for equipment leaks, and the wastewater CTC document
methodology for wastewater. Example calculations are given in
Appendix A.
National emissions from paint stripper formulators were estimated
to be 26,500 Mg/yr in 1988. As of the 1987 study, there were no State
regulations requiring emissions reductions. Therefore, implementation
of emission controls in the industry were not common at that time.
Emissions were separated into emissions from storage, handling,
equipment leaks, and secondary sources; emissions estimates are shown
in Table 12. The typical model plant emitted about 179 Mg/yr, and
178 Mg of this was from handling (mostly mixing tank) emissions.
However, individual plant emissions ranged from about 7 to over
7,000 Mg/yr.
Lower MC content products are currently being developed because
of worker exposure issues and consumer demand.4 Reduction in emissions
may occur as paint stripper formulations are developed with lower
MC content. However, estimates of emissions reductions that may
result from lowering the MC content of finished products have not been
made.
Paint Stripping Processes--
For each type of paint stripping process, emissions are
segregated into three categories; building openings, process vents,
and outdoor storage. Emissions from most paint stripping processes
are released through building openings or other openings, such as
windows and doors. Other building opening sources include general
maintenance operations.
Emissions from these sources were estimated in 1987 during a
previous EPA project.2 The data are more extensive for larger, well-
defined industries. Paint stripping emissions estimates are not
available for commercial (e.g., metal, office, residential) furniture
facilities. In general, a material balance approach was used to
45
-------
TABLE 12. ESTIMATED METHYLENE CHLORIDE EMISSIONS FROM PAINT STRIPPER FORMULATORS (1988!
Methylene Chloride Emissions
Equipment
Company Name
Benco Sales Inc.
Benco Sales Inc.
Hillyard Chemical Co.
Jasco Chemical Corp.
Kwick Kleen Industrial
Pennwalt Corp. (Turco)
Pennwalt Corp. (Turco)
Sherwin Williams Co.
Sherwin Williams Co.
Star-Bronze
Stripping Products (Bix
W.M. Barr and Co., Inc.
Model Plant13
TOTALC
Location
Crossville, TN
Fontana, CA
St. Joseph, MO
Mountain View,
SolventsnSennes , IN
Carson, CA
Marion, OH
Chicago, IL
Richmond, KY
Alliance, OH
Total Storage
87.3
33.3
140.6
CAL 1 0 . 6
6.9
17.9
25.2
44.4
434.7
134.1
) Old Hickory, TN 7.2
Memphis, TN
7,046.8
178.8
26,500
2.
2.
4.
3.
2.
1.
1.
2.
0
9.
1.
0
0.
92
5
1
2
8
4
6
.2
.5
.7
.3
.6
(Mg/yr)a
Leaks
Handling outdoor Indoor s«
83.
30.
136.
105.
4.
14.
23.
40.
433
123
3.
7,044
177
6
1
.3
.4
5
9
0
6
.9
.1
9
.0
.9
26,010
0.8
0.8
0.06
1.0
0
1.0
1.0
1.0
0.8
0
2.0
2.2
0.26
31
0.
0.
0.
0.
0.
0.
0
0
0
1
0
0
0
9
.03
.04
.04
.3
.01
.4
.1
.3
.03
.3
.007
.6
.06
.3
Accidental
scondary Releases
NR
NR
NR
NR
NR
0.03
NR
NR
NR
NR
NR
NR
NE
0.03
0.3
0.2
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NE
0.5
a "NR" means no emissions were reported in the questionnaire response. "NE" means emissions were not estimated.
b The model represents each of the 101 paint stripper formulation facilities that did not receive a
questionnaire. See Appendix B for a list of these companies. Emission estimates for the model plant were
developed from the questionnaire responses completed by the 12 facilities.
c The total emission estimates represent emissions from all 113 paint stripper formulators.
-------
estimate emissions from each type of stripping process. Tanks were
assumed to contain only MC for purposes of estimating emissions.
Because paint strippers contain other compounds, such as waxes to
retard evaporation, this assumption may slightly overestimate these
emissions.
Emissions from use and storage of paint strippers inside
buildings are emitted through building openings. For general
maintenance and other miscellaneous uses, it was assumed that all of
the MC consumed is emitted to the atmosphere. For indoor storage
tanks, emissions were calculated using AP-42 equations for fixed-roof
storage tanks; the emissions would be released from building openings.
Process vents, such as vents that are routed to the atmosphere
from spray booths in automobile assembly, are generally considered to
have emissions equal to the rate of MC consumption.
Outdoor storage emissions were based on AP-42 equations for
fixed-roof storage tanks. However, many facilities store MC in
55-gallon drums, for which emissions are negligible.
The national total emissions for consumers of MC for paint
stripping purposes were estimated at 41,900 Mg/yr in 1987. Emissions
from each industry are discussed below.
Automobile assembly emissions of MC that were received in
response to a Section 114 questionnaire in 1987 are presented in
Table 13. In a previous study, an emission factor was derived from an
emissions-to-consumption ratio based on the questionnaire responses,
and was applied to all automotive facilities not included in the
survey. This emission factor was 0.8 Mg MCe/MCc, where MCe and MCC
represent MC emitted and consumed, respectively.3 Total national
emissions in 1987 from automotive facilities were then estimated to be
12,320 Mg/yr.
Aircraft maintenance facilities emissions are estimated by an
emission factor derived from material balance. The total emissions
47
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TABLE 13. ESTIMATED METHYLENE CHLORIDE EMISSIONS FROM
TWELVE AUTOMOBILE MANUFACTURING FACILITIES, 1987a
Methylene Chloride
Company Name Location
General
Motors
General
Motors
General
Motors
General
Motors
General
Motors
General
Motors
General
Motors
General
Motors
General
Motors
General
Motors
General
Motors
Ford
TOTAL
Anderson, IN
Atlanta, GA
Baltimore, MD
Bowling Green,
KY
Columbus , OH
Flint, MI
Kansas City,
MO
Lordstown, OH
Moraine, OH
Pontiac, MI
Shreveport , LA
Ypsilanti, MI
Process
Vents
0
102.0
124 .0
9.4
0
9.7
46.1
199.2
199.2
19.8
33.1
0
742 .5
Building
Vents
10.5
0
0
0
196.8
48.7
7.4
95.5
95.5
0
0
0.2
454 .6
Emissions (Mg/yr)
Outdoor
Sources
0
0
0
0
Ob
0
0
0
0
0
1.9C
0
1.9
Total
10
102
124
9
196
58
53
294
294
19
35
0
1,199
.5
.0
.0
.4
.8
.4
.5
.7
.7
.8
.0
.2
.0
Source: Reference 3.
a This table represents MC emissions estimated only for those
automobile manufacturing facilities that completed a Section 114
questionnaire response.
b The storage tank at this facility is an outdoor tank and is
reportedly controlled; however, insufficient information was
available to estimate emissions.
c Outdoor dip tank.
48
-------
for this industry in 1987 were estimated to be 4,720 Mg/yr MC using
the same emission factor (0.8 Mg MCe/MCc) that has been used in the
automotive sector, since the process is similar.
Military emissions can be from a variety of sources. The largest
sources identified are aircraft and automobile maintenance. For these
activities, emission estimates of 40 percent and 80 percent of MC
consumed were applied to all facilities with and without dip tanks,
respectively. The 80 percent figure is derived from the data in the
aircraft and automotive section.3 Dip tanks are used for most military
paint stripping operations. Nationwide military consumption of MC has
been estimated at 14,500 Mg/yr.3 Emissions have been estimated to be
6,400 Mg/yr using a combination of the 40 percent and 80 percent
emission factors. Emissions identified for individual facilities are
presented in Table 14.
Household uses consumed approximately 13,200 Mg/yr of MC in
1987.3 Household emissions are estimated using the material balance
approach. The amount emitted is assumed equal to the amount of MC in
the product, usually 80 to 90 percent.6 The emissions-to-consumption
ratio (emission factor) for household use as well as automobile and
aircraft use is shown in Table 15.
Emission control techniques can be generally applied to each
segment of the users of paint strippers, with the exception of
household use. Refrigerated condensers and carbon adsorbers may be
installed, and obtain similar emission reduction efficiency to that
indicated for paint stripper formulators. These can be used for
vented storage tanks and stripping operations. Floating roofs may
also be applied to fixed-roof storage tanks. Dip tanks may also
incorporate increased water cover and drain time as well as a carbon
adsorber. The emission reduction efficiency for dip tank controls is
from 50 to 60 percent. The efficiencies of these techniques are
summarized in Table 16.3
The overall efficiency of emission controls at automotive and
aircraft maintenance facilities have both been estimated to be
70 percent, based on two automotive manufacturing plants and seven
aircraft hangars.3 The commercial furniture industry is estimated to
obtain a 20 percent reduction in emissions by using controls on dip
tanks.3
49
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TABLE 14. ESTIMATED METHYLENE CHLORIDE EMISSIONS FROM
LARGE-SCALE MILITARY USERS OF PAINT STRIPPER,
1987
Methylene Chloride Emissions
(Mg/yr)
Installation
Anniston Army
Bergstrom
Name
Depot3
City
Anniston
Austin,
, State
, AL
TX
Process
Vents
0
0
Building
Vents
14
107
Outdoor
Sources
0
0
Total
14
107
Air Force Base
Corpus Christ!
Army Depot3
Hill Air Force Base
Kelly Air Force Base
Letterkenny
Army Depot
McClellan
Air Force Base
Corpus Christ!, TX
Ogden, UT
San Antonio, TX
Letterkenny, PA
Sacramento, CA
45
45
Naval
Aviation Depot3
Naval Aviation Depot
Naval Aviation Depot
Naval Shipyard3
Robins
Air Force Base3
Tinker
Air Force Base3
Tooele Army Depot
Wright -Patter son
Air Force Base
Model Plant13
TOTAL0
Cherry Point, NC
Jacksonville, FL
Pensacola, FL
Philadelphia, PA
Warner Robins, GA
Oklahoma City, OK
Tooele, UT
Dayton, OH
0
0
0
0
0
0
0
0
0
0
14
68
64
4.7
247
256
2.8
1.6
550
6,400
0
0
0
0
0
0.
0
0
0
0.
14
68
64
4.
247
.2 256
2.
1 .
550
.2 6,400
.7
.8
.6
Source: Reference 3.
3 Detailed information available for this facility based on questionnaire
response or site visit.
b The model represents each of the nine Naval installations not listed
individually in this table, that are large-scale users of MC-based paint
stripper, but for which MC consumption data are unavailable.
c The total emission estimates represent emissions from all 24 military users
of MC for large-scale paint stripping operations.
50
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TABLE 15. PAINT STRIPPING EMISSIONS FACTORS
Paint Stripping Application Emission Factor3
Automobile facilities 0.8
Aircraft maintenance 0.8
Military installation dip tanks 0.4
Household uses 1. 0
1 Units are Mg emitted/Mg consumed in paint stripper.
51
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TABLE 16. ADDITIONAL CONTROL TECHNIQUES FOR EMISSIONS OF
METHYLENE CHLORIDE SOLVENTS FROM PAINT STRIPPER
USERS
Emission Source
Additional Controls
Control
Efficiency
Storage Tank
Stripping in Large, Open
Areas
Stripping of Paint Spray
Booths
Dip Tank
Refrigerated Condenser
Enclosure and Carbon
Adsorption
Carbon Adsorption
Water Cover and
Increased Drain Time
Carbon Adsorber6
95a
95b
95b
60c'd
50d
a Reference 8.
b Reference 9.
c Percent reduction in MC emissions based on reduction efficiencies
estimated for cold cleaners in the organic solvent cleaning source
category.
d Reference 10.
e This control option only applies to one dip tank that is operated
like an open-top vapor degreaser.
52
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REFERENCES FOR PAINT STRIPPER INDUSTRY
1. "Paint--Tests for Formulated Products and Applied Coatings," 1990
Annual Book of ASTM Standards, Volume 06.01, R. Storer, et al,
eds. American Society for Testing and Materials, Philadelphia,
PA, 1990.
2. "Emission Estimates and Controls for Emissions from Paint
Stripper Formulation Facilities (DRAFT)," Memorandum from E.
Moretti, Radian Corporation, Research Triangle Park, NC, to the
U.S. Environmental Protection Agency, Research Triangle Park, NC,
September 11, 1987.
3. "Emissions, Controls, and HEM Inputs for Paint Stripping,"
Memorandum from C. Most, Radian Corporation, Research Triangle
Park, NC, to the U.S. Environmental Protection Agency, Research
Triangle Park, NC, December 18, 1987.
4. White Paper -- Methylene Chloride. Halogenated Solvents Industry
Alliance, Washington, DC, February 1989.
5 . Occupational Safety and Health Administration Proposal for New
Methylene Chloride Standard, 56 FR 57049, November 7, 1991.
6. "Impact of Pending VOC Limits in Paints and Coatings," Memorandum
from John Forrester, Radian Corporation, Research Triangle Park,
NC, to Brian Palmer, Radian Corporation, Research Triangle Park,
NC, April 20, 1992.
7. "Summary of Information Obtained Through Telephone Contact with
Formulators, Distributors, and Users of Methylene Chloride-Based
Paint Strippers," Memorandum from I. McKenzie, Radian
Corporation, Research Triangle Park, NC, to the
U.S. Environmental Protection Agency, Research Triangle Park, NC,
January 22, 1987.
8. Control Technologies for Hazardous Air Pollutants, EPA-625/6-86-
014, U.S. Environmental Protection Agency, Research Triangle
Park, NC, September 1987.
9. "Assessment of Carbon Adsorbers for Control of Hazardous Air
Pollutants," Memorandum from P. May and G. Bockol, Radian
Corporation, Research Triangle Park, NC, to L. Evans,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
December 1, 1986.
10. "Summary of Emission Reductions Achievable by Applicable Control
Techniques for Organic Solvent Cleaners," Memorandum from S.
Miller and R. Pandullo, Radian Corporation, Research Triangle
Park, NC, to Degreasing NESHAP File, October 21, 1987.
53
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54
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PLASTICS MANUFACTURING
Methylene chloride is used in the manufacture of polycarbonate
resin, triacetate fiber, and other plastics. The processes and MC
emissions for production of these materials are discussed below.
Polycarbonate Resins
Polycarbonates are a special class of polyesters derived from the
reaction of carbonic acid derivatives with aromatic, aliphatic, or
mixed diols. Polycarbonates are useful for their high impact strength,
transparency, low flammability, and toughness. These qualities make
them desirable for products that are subject to sudden loads, such as
safety helmets, tool housings, appliances, and food dispensing
equipment; and also for transparent items such as windows, automotive
lenses, safety glasses, and bottles. Polycarbonates are used in
greenhouses and for solar energy collection in commercial and
residential applications. Medical devices are also made from
polycarbonate because it can be sterilized both by autoclave and gamma
radiation. Other uses for polycarbonate resins are in computers,
aircraft, telephones, and business equipment.
Polycarbonate resins were manufactured by four producers in 1991:
General Electric in Mount Vernon, Indiana; Bayer U.S.A. (Mobay
Corporation) in Baytown, Texas; Dow Chemical in Freeport, Texas; and
Mobay in New Martinsville, West Virginia.1
Process Description--
A process flow diagram for polycarbonate resin production is
shown in Figure 4. Polycarbonates may be produced by the Schotten-
Baumann reaction of phosgene with a diol in the presence of an
appropriate HC1 acceptor [e.g. bisphenol-A (BPA) with phosgene in the
presence of an excess of pyridine], or by a melt transesterification
reaction between the diol and a carbonate ester. Transesterification
is reported to be the least expensive route; however, that process has
been phased out because there were many polycarbonate products that
could not be produced using transesterification.
55
-------
Methylene
Chloride
Storage
Cooling Water
Water + HCI
Precipitant
Bisphenol-A
Pyridine Storage
Reactor
Cooling Water
Phosgene
Wash Tank
Aqueuos Phase
NaOH
Polycarbonate
Methylene Chloride
Precipitation
Methylene Chloride Recycle
Methylene Chloride Recycle
Crystalline
Polycarbonate
Dryer
Hot Air
Polycarbonate
Product
Preparation
Product
Pyridine
Recycle
Azeotropic
Distillation
NaCI
Source: Reference 2
Figure 4. Process flow diagram for the production of polycarbonate resin.
56
-------
Generally, the interfacial process is used in the production of
polycarbonate resins. During polymerization, a jacketed vessel
equipped with an agitator is charged with the reactants and MC
solvent. Phosgene gas is bubbled through the reactor contents. The
reaction requires approximately 1-3 hours and is carried out at
temperatures below 40°C (104°F). Pyridine and MC are recycled during
the process.
The polymerized-liquified reactor contents are then pumped to
wash tanks to remove residual pyridine using HC1 and water. Methylene
chloride is removed by steam stripping. The polycarbonate polymer is
precipitated from the polymer-MC stream with an organic compound such
as an aliphatic hydrocarbon and is separated by filtration. The
filtered polymer is transferred to a dryer, while the solvent is
recovered in a distillation column.
Both General Electric and Bayer now use the interfacial process
described above. In this process, the BPA is dissolved as a disodium
salt in aqueous caustic and reacted with phosgene bubbled into an MC
layer. Reaction occurs at the solution's interface with the polymer
"growing" into the MC layer. The MC layer is then separated, and the
polymer is isolated by removal of solvent. At this stage, the various
producers use a number of different processes, including
devolatilization extrusion, granulation, and spray drying.
General Electric-PBG is the largest U.S. manufacturer of
polycarbonate resin. At the GE BPA manufacturing plant, MC is a
recrystallization solvent for BPA. Recrystallized BPA is dried and
fed to the polycarbonate resin production process. Methylene chloride
is captured and recycled back for reuse, at an overall recovery rate
of 99.5 percent. Primary recovery means include low-temperature
condensation and carbon adsorption with regeneration. General
Electric is currently planning to make the BPA production process
solventless by using a melting process instead of the MC
recrystallization process to produce BPA.
At the General Electric polycarbonate resin plant, MC is also
used as a process solvent to carry polycarbonate polymer through the
reaction and purification process. The polycarbonate resin is then
57
-------
isolated and the MC is recovered through a distillation process and
recycled. Numerous process vents are combined and routed to vent
absorbers. The overall MC recovery rate in this operation is
99.8 percent.
At the General Electric polycarbonate-polysiloxane resin plant,
which is small compared to the polycarbonate resin plant, MC is also
used as a process solvent in the operation. At this operation, the
overall MC recovery rate is approximately 93 percent.
As indicated above, the use of MC is a critical element in
maintaining product quality and safety specifications. Also, other
solvents may crystallize, craze, crack, or mar the surface of objects
made from polycarbonates.1
Emissions*--
Emissions from polycarbonate resin production are from process
vents, equipment leaks, storage, handling, equipment openings, and
secondary sources. Information on estimated 1983 MC emissions from
the Mount Vernon General Electric and Baytown Mobay facilities was
obtained; however, more recent emissions data on these facilities
could not be located, nor could emissions data for the Freeport Dow
Chemical, or New Martinsville Mobay, plants. Emission sources,
controls, control efficiencies, and emission quantities for the Mount
Vernon General Electric and Baytown Mobay facilities in 1983 are
presented in Table 17.
General Electric reported that the production of polycarbonate
resins and proprietary associated processes at the Mt. Vernon facility
resulted in 3,578 Mg of MC emissions in 1983. The company indicated
that emissions reported for individual sources were either rough
estimates or maximum allowable permitted levels and that it could not
give exact values for each emission source. General Electric reported
four process areas emitting MC. Two of the process areas used MC in
polycarbonate synthesis; the other two
Information presented in this section on emissions from
polycarbonate resin production was obtained from Reference 2.
58
-------
TABLE 17. ESTIMATED 1983 EMISSIONS AND CONTROLS AT FACILITIES USING
METHYLENE CHLORIDE IN POLYCARBONATE RESIN PRODUCTION
Company/
Location Type of Emissions
General Electric Process
Mount Vernon, IN • Hopper Dryers
• Hopper Dryers
• Extruder Die Hoods
• Extruder Die Hood
• Extruder Die Hood
• Extruder Die Hood
• Extruder Die Hood
• Extruder Die Hood
• Molding Machine Vents
• Q.A. Hood Vent
• Extruder Die Vents
• Extruder Vacuum Pump
• Extruder/Die Vent
• Extruder/Die Vent
• Molding Machine
• Vacuum Stripping
Blowers
• Vent Gas Absorber
• Vent Gas Absorber
• Carbon Adsorption
System
• Filter Receiver
• Filter Receiver
• Weight Hopper Vent
Reported
Control
Controls Efficiency (%)
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
Water Scrubber
Water Scrubber
Carbon Bed
None
None
None
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
87
87
87
0
0
0
MC
Emissions
(Mg/yr)
17.
18.
224.
4
2
8
13
0
4
6
391
86
11
93
3
0
477
477
46
85
85
0
.0
.6
,6
.5
.5
.8
.4
.2
.8
.4
.4
.2
.8
.2
.6
.3
.3
.2
.6
.6
.6
Comments
41 dryers
45 dryers
7 hoods
1 hood
1 hood
1 hood
1 hood
1 hood
2 vents
4 vents
17 vents
6 pumps
3 vents
8 vents
2 units
4 units
1 vent
1 vent
2 units
2 units
2 units
-------
TABLE 17. (CONTINUED)
Company/
Location
GE, Mount Vernon
(Cont'd)
TOTAL
Mobay Chemicals,
Baytown, TX
Type of Emissions
• Feed Hopper
• Surge Hopper
• MC Storage Tank
• Storage Silo
• Solvent Recovery
• MC Dryer System
• Tar/Isomer Storage
Equipment Leaks
• Building 14/16
• Building 15/31
Storage
• 44 process and storage
vessels
• Pressure vessel
Equipment Opening
Secondary
• Biological Treatment
Process
• Vent
• Reactor Vent
• Reactor Vent
Controls
None
None
Conservation Vent
None
Carbon Bed
Knock Out Pot/
Demister
None
Photo ionization
detection system
Photo ionization
detection system
Vent gas absorbers
Conservation vent
None
None
Scrubber
None
None
Reported
Control
Efficiency (%)
0
0
10
0
87
50
0
0
0
87
10
0
0
98
0
0
MC
Emissions
(Mg/yr)
0.3
7.6
17.6
170
347
79.6
0.4
175
71.8
0.1
1.5
63 .7
584
3,578
0.3
0.07
0.05
Comments
1 unit
2 units
Monitors 40 points
Monitors 10 points
Bldg 14/16
Bldg 15/31
-------
TABLE 17. (CONTINUED)
Company/
Location Type of Emissions
Mobay Chemicals Equipment Leaks
(Cont'd)
Equipment opening
Storage
• Fixed-Roof Tank
• Fixed-Roof Tank
• Fixed-Roof Tank
• Fixed-Roof Tank
• Fixed-Roof Tank
Secondary
• Wastewater stream
• Contained solvent
• Process water trench
• Leaks and spills
Handling
• Railcar, tank truck
TOTAL
Reported
Control
Controls Efficiency (%)
Monthly portable gas
chromatograph check,
pressure relief
device controls
None
Vent to scrubber
Vent to scrubber
Vent to scrubber
Vent to scrubber
Vent to scrubber
Biological & Carbon
Treatment
Incineration
Biological & Carbon
Treatment
None
None
NR
0
98
98
98
98
98
NR
NR
80
0
0
MC
Emissions
(Mg/yr)
51.
16.
0
0
0
0
0
22
0
11
41.
0
143
.2
.5
.006
.006
.1
.1
.003
.0
.0
.4
.6
Comments
Primarily sampling openings
27,100 gallons
150,000 gallons
85,200 gallons
85,200 gallons
27,100 gallons
Source: Reference 2.
-------
areas were used in polycarbonate processing, and MC emissions resulted
from residual in materials processed.
Process vents were the source of 75 percent of the total
MC emissions for this plant. Many of the smaller vents were
uncontrolled, but some of the larger vents were controlled by
scrubbers or carbon adsorbers, achieving 87 percent control.
The second largest MC emission source at General Electric was
secondary sources (16 percent). General Electric estimated that
approximately 1,818 kg/day MC was discharged to the site sewer system.
Approximately 218 kg/day reached the wastewater treatment plant for
on-site biological treatment. The remaining 1,600 kg/day were lost to
the atmosphere in three areas: (1) the brine recovery operation,
(2) the sewer system, and (3) the wastewater treatment plant prior to
biological treatment. As discussed in Section 4, emissions from
wastewater prior to treatment can be reduced by using covers and
enclosures, either alone or with a closed-vent system and control
device.
Equipment leaks were the third largest source of emissions (7
percent) generated at the General Electric plant. Equipment counts
were reported for two of four process areas; the other two process
areas did not have equipment in MC service, and emissions resulted
from residual MC in the materials processed. General Electric
reported that multipoint programmable sequence area monitoring was
performed to detect MC leaks using a photo ionization detection HN|i
system. However, because it did not report the frequency of repair,
uncontrolled emission factors were used to estimate equipment leak
emissions, possibly resulting in an overestimate. Leak detection and
repair programs can reduce emissions from equipment leaks.
General Electric based the equipment openings emissions estimate
on field estimates of quantities in the system at the time of opening.
Emissions were extrapolated using the number of occurrences and
assuming 100 percent loss.
The polycarbonate resin process generated 143 Mg of MC emissions
at Mobay Chemical in Baytown, Texas, in 1983. Table 17 documents
62
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emission sources, controls, control efficiencies, and 1983 emission
amounts for this facility.
Secondary sources were the largest source of MC emitters at
74.4 Mg/yr. Mobay listed three sources for these emissions: (1) a
wastewater stream going to biological and carbon treatment (22.1 Mg) ;
(2) a process water trench also going to biological and carbon
treatment (10.9 Mg); and (3) other leaks and losses prior to
maintenance work (41.4 Mg).
Emissions from equipment leaks were 51.2 Mg in 1983. Mobay had
33 pressure relief devices protected by rupture disks. Twenty more
relief valves were vented to a scrubber to control emissions, and five
pressure relief valves were unprotected.
Mobay's recorded process variables each shift to detect obvious
leaks. Also, a daily walkthrough was performed to spot leaks. A
solvent inventory was taken each week to account for any unusual loss.
All pump seals and vent locations were checked monthly with a portable
gas chromatograph. In addition, one technician devoted half-time to
solvent loss prevention. Mobay believed this monitoring system was
reasonably effective for obvious losses. Mobay did not report the
frequency of leak repairs, and emissions from equipment leaks were
calculated using uncontrolled emission factors. Therefore, these
emissions may be overstated.
Losses from equipment openings were 16.5 Mg in 1983.
Forty-four percent of equipment openings losses were due to daily
sampling. Mobay reported that approximately 50 samples are taken per
day. Filter replacement contributed about 37 percent of MC emissions.
Replacement of an 80,000-gallon product tank emitted 1.6 Mg. Other
equipment opening losses were due to routine maintenance of
purification equipment, pump seal replacement, heat exchanger
replacement, and from opening open solvent lines to remove pluggage.
Solvent handling losses were 0.6 Mg/yr. Methylene chloride was
delivered by railcar and/or tank truck. No control equipment was used
to reduce emissions during unloading.
63
-------
Emissions from three process vents totalled 0.4 Mg in 1983. A
process vent scrubber operating at 98 percent MC removal efficiency
emitted 0.3 Mg MC. The emission level was determined from inlet and
outlet sampling and gas chromatograph analysis of the samples for
composition. Two reactor vents that emitted MC only when the reactor
was being filled had a combined annual loss rate of about 0.1 Mg/yr.
Emissions occurred from these vents for only about 10 minutes per
month.
Losses from five fixed-roof storage tanks were about 0.2 Mg in
1983. All storage tank conservation vents were vented to a scrubber.
Mobay reported that sampling indicated that this control technique
reduced emissions by 98 percent.
Information on the amount of MC used or the amount of
polycarbonate resin produced at the Mobay and General Electric
facilities was not available to allow development of emission factors
per unit of MC used or per unit of product produced. However, as
discussed in depth under MC production, storage and handling emission
factors can be derived by using information on the types of storage
tanks and transfer equipment found at a specific site to select the
appropriate factors for that site from EPA Publication No. AP-42.
Also as described in Section 4.0, the methodologies presented in
"Protocols for Generating Unit-Specific Emission Estimates for
Equipment Leaks of VOC and VHAP" (volatile hazardous air pollutant)
can be used to estimate emissions from equipment leaks. An example of
one of the simpler methodologies is presented in Appendix A,
Section 2. Emissions of MC from wastewater can be estimated using
site-specific data with the methodology presented in the EPA CTC
document on VOC emissions from industrial wastewater.
Triacetate Fiber
Methylene chloride is used by one company, Celanese Corp., in
Cumberland, Maryland, as a solvent for spinning cellulose triacetate
fibers. It is estimated that all of the approximately 2.0 Mg of MC
used at this facility are released to the air. Methylene chloride,
which is an excellent and inexpensive solvent for the production of
secondary acetate, has been used for triacetate production since 1930.
Nearly all of the cellulose triacetate is used for ladies' apparel.
64
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Much of it is used to make 100 percent continuous-filament open
fabric. High bulk Tricel is used in knitwear.1
Process Description--
No information was located on the triacetate fiber manufacturing
process used at Celanese's Cumberland, Maryland, facility. However, a
1985 process description was obtained for its Rock Hill, South
Carolina, plant, which is no longer producing triacetate fiber.
A solution of MC and methanol is fed into a batch mixer
containing triacetate polymer flakes and other dry ingredients. The
solvents are slowly mixed with the solids until the solids are
completely dissolved, forming the liquid polymer dope. The dope is
then filtered and pumped to the extrusion area, where it is preheated,
and then extruded and dried. The dried fibers are spun onto bobbins
until further processing is performed, which may include twisting,
coning, and beaming.2 A process flow diagram is shown in Figure 5.
Solvents that can be substituted for MC in the manufacture of
cellulose triacetate are chloroform, formic acid, glacial acetic acid,
dioxan and cresol.1
Emissions--
No information was located on emissions of MC from triacetate
fiber manufacture at the Celanese Cumberland, Maryland, plant.
Estimated emissions from the Rock Hill, South Carolina, plant in 1983
are given in Table 18. It is not known whether this information is
representative of the current MC emissions, sources, and controls at
the Cumberland, Maryland, plant. Because of lack of information,
emission factors could not be developed for this process. As
discussed in depth in Section 4, EPA methods from the AP-42 and
"Protocols" documents can be used with site-specific data to develop
emissions estimates for storage, transfer, and equipment leak
emissions from triacetate fiber production.
65
-------
Methylene
Chloride
Triacetate
Polymer
Flake
Filter
Extrusion
ON
r+
Bobbin
Bobbin
Transport
Bobbin
Storage
Textile
Department
Twisting
Coning
Beaming
-*• Storage
Source: Reference 2
Figure 5. Process flow diagram for the production of triacetate fibers.
-------
TABLE 18. ESTIMATED METHYLENE CHLORIDE EMISSIONS AND CONTROLS
ASSOCIATED WITH TRIACETATE FIBER MANUFACTURE3
Types of
Emissions
Process
• Solvent
recovery
Equipment
leaks
Transfer
• Tank
truck,
tank car
Relief
devices
Controls
Carbon
adsorption
Infrared gas
analyzers
Vent to
solvent
recovery
NA
Reported
Control
Ef f icienc
y (%)
98b
0
NR
MC
Emission
s
(Mg/yr)
5,150
22 .0
0.5
2 .7
Comments
Mixture rupture
discharge
Emissions data apply to a Celanese chemical plant in Rock Hill, S.C.
in
1983 . Data taken from Reference 2 .
b Greater than 98 percent efficiency reported, but only 98 percent is
accepted
without supporting test data.
67
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Plastics Production
In 1983, the General Electric facility in Pittsfield,
Massachusetts, was reported as using MC in a plastics production
operation.2 Current data verifying the continued use of MC at this
plant could not be located, nor could data on the use of MC for
plastics production at other facilities.
Process Description--
At the time the 1983 information was gathered on plastics
production at its Pittsfield, Massachusetts, plant, General Electric
considered information on process description and end products
confidential.2 Because non-confidential information from other plants
was not located, descriptions of processes using MC in plastics
production are not available.
Emissions*--
Process vents and equipment leaks were the major emission sources
at the General Electric facility. It also reported emissions from
secondary sources, storage tanks, and equipment openings. Transfer
emissions were unknown at that point because the facility had just
instituted a new bulk handling system for pumping solvent from tank
trucks into on-site storage tanks. Emission sources, controls,
control efficiencies, and emission levels for 1983 are presented in
Table 19.
Total MC emissions at this facility were 74.0 Mg in 1983.
Emissions from process vents were 64.9 Mg of MC (88 percent of total
MC emissions). General Electric reported 13 process vents, with three
vents controlled by condensers. A precipitation condenser vent and a
dryer vacuum pump were both controlled by condensers operating at
50 percent MC removal efficiency. Emissions from these vents after
control were 27.2 Mg and 9.8 Mg, respectively. The precipitation
condenser vent was the largest single MC emission point at the
facility. An MC still vent was controlled by a condenser operating at
97 percent removal efficiency. Emissions from this vent were 8.2 Mg.
Information presented in this section on emissions from plastics
production was obtained from Reference 2.
68
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TABLE 19.
ELECTRIC,
ESTIMATED METHYLENE CHLORIDE EMISSIONS AND CONTROLS
ASSOCIATED WITH PLASTICS PRODUCTION AT GENERAL
PITTSFIELD, MASSACHUSETTS IN 1983
Types of
Emissions
Process
• Reactor vent
• Phosgenation
reactor
• Precip. room vent
• Work -up room vent
• Stripper room vent
• Stripper room vent
• Precip. condenser
vent
• MC still water tank
• Area vent
• MC still vent
• MC/water separator
• Still decant tank
• Dryer vacuum pump
Equipment leaks
Storage
• Fixed-roof tank
• Fixed-roof tank
• Fixed-roof tank
• Fixed-roof tank
• Fixed-roof tank
• Fixed-roof tank
Equipment Opening
Secondary
• Aqueous waste
stream
• Drums
Reported
Control
Ef f icienc
Controls y (%)
None
None
None
None
None
None
Condenser
None
None
Condenser
None
None
Condenser
None
To Condenser
None
None
To Condenser
To Condenser
None
None
To Sewage Treatment
To Haz. Waste
Disposal
0
0
0
0
0
50
0
0
97
0
0
50
0
50
0
0
50
50
0
0
80
90"
MC
Emission
s
(Mg/yr)
4.6
2.4
1.8
1.3
1.8
1.8
27.2
0.9
2.7
8.2
1.8
0.5
9.8
6.1
0.09
0.06
0.06
0.007
0.1
0.005
2.3
0.1
0.01
Comments
Leaks detected by
observation and weekly
mass balance
4,100 gallons
500 gallons
500 gallons
1,500 gallons
1,250 gallons
250 gallons
a Greater than 98 percent efficiency reported, but only 98 percent is accepted
without supporting test data.
Source: Reference 2.
69
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The 10 remaining process vents were uncontrolled. Emissions ranged
from 4.6 Mg for reactor area ventilation to 0.9 Mg for the
MC still-water tank.
Equipment leaks resulted in MC emissions of 6.1 Mg/yr. Valves
emitted approximately 3.1 Mg of MC (51 percent). Pump seals and
flanges emitted 1.0 Mg (16 percent) and 0.8 Mg (13 percent),
respectively. General Electric reported that there was no automated
leak detection system for MC. Any significant MC leaks were generally
determined by operator observation. Also, a weekly mass balance
inventory was maintained for MC usage. Substantial increases over the
normal process usage requirements initiated a full system
investigation to determine if any leakage was occurring.
Equipment opening losses were approximately 2.3 Mg in 1983.
General Electric estimated this loss for approximately 2,000 openings,
1,300 of which were an end-cap reactor nozzle opened during each batch
to add reactants. In addition, another reactor nozzle is opened
650 times per year. Other equipment openings involved work-up tanks,
Westfalia centrifuges, filter feed tanks, filters, MC stills, and
separator/decant tank. General Electric provided an overall equipment
opening loss estimate, but did not identify emissions by specific
sources.
General Electric maintained six fixed-roof storage tanks
containing MC. The emissions from these tanks totalled 0.3 Mg/yr.
The tanks ranged in volume from 250 to 4,100 gallons. Three of the
tanks were vented to a vent condenser with 50 percent control
efficiency. Emissions from two other tanks were piped to a controlled
tank, while one tank was uncontrolled.
A bulk handling system for MC was instituted in 1983. Tank truck
deliveries were made to a fixed-roof, 4,100-gallon storage tank. The
tank car feed line was connected to a pump at the storage tank base
and delivered into the storage tank. Vapors were piped to the plant
vent system, which condensed most of the MC vapors. General Electric
reported air intake was through a canister and a vacuum relief valve.
Two waste streams emitted about 0.2 Mg of MC in 1983. The major
secondary emission source was a liquid stream to the sewage treatment
70
-------
plant, which emitted 0.15 Mg of MC. A second waste stream was
unidentified. This stream is contained in drums that were sent to a
licensed hazardous waste disposal company. Emissions (0.01 Mg)
occurred when the waste stream was transferred to drums.
Because of the lack of information about the actual production
process, emission factors on a per-MC-used or per-product-produced
basis could not be developed. As described in Section 4.0 on
production, the methodologies presented in "Protocols for Generating
Unit-Specific Emission estimates for Equipment Leaks of VOC and VHAP"
(volatile hazardous air pollutant) can be used to estimate emissions
from equipment leaks. An example of one of the simpler methodologies
is presented in Appendix A. Storage and handling emission factors can
be derived by using site-specific information on the types of storage
tanks and transfer equipment to select the appropriate factors from
EPA Publication No. AP-42.
71
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REFERENCES FOR PLASTICS MANUFACTURING
1. Occupational Safety and Health Administration Proposal for New
Methylene Chloride Standard, 56 FR 57047, November 7, 1991.
2. Survey of Methylene Chloride Emission Sources, EPA-450/3-85-015,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
June 1985.
72
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FLEXIBLE URETHANE FOAM PRODUCTION INDUSTRY
Polyurethane products are generally complex plastics that form
from a reaction of liquid isocyanate components with liquid polyol
resins.1 The resin component can also contain blowing agents,
combustion retarding agents, and catalysts. Polyurethane products
include polyurethane foams, flexible polyurethane foams, and
polyurethane elastoplastics.1 Polyurethane foams are solid.
Methylene chloride is the leading auxiliary foam-blowing agent
used in the production of flexible urethane foams. Its use in the
foam industry is largely in the production of flexible slabstock foam.2
It also has some use in the production of flexible molded foam.3 The
development of new catalysts enabled the use of MC in a variety of
foam formulations.
Methylene chloride is considered to be a physical blowing agent
(also known as "solvent") that assists in foam cell formulation, as it
is a low boiling point (39.8°C) halogenated hydrocarbon that does not
decompose.3'4 There are indications that MC is also used to clean the
molding and the foam mixing head, and as a carrier solvent for the
mold release agent.3
There are an estimated 180 foam-blowing companies in the United
States, including slabstock and flexible molded foam companies.1 In
1991, these companies consumed approximately 14 percent of the total
MC production.2 Polyurethane foam industry consumption of MC in 1984
was estimated to be 70 percent slabstock urethane foam and 30 percent
flexible molded foam, derived from Halogenated Solvents Industrial
Alliance (HSIA) data and Section 114 questionnaires.3 The 1991
estimate shows a 20 percent increase in use in polyurethane foam
production from the 1984 estimate. Flexible urethane molded foam
facilities were not located at that time because this product was
considered to be a less significant source of MC emissions. The
present location of all existing foam-blowing facilities was not
determined. The following sections will discuss the industry
production processes, emission sources, and emission estimates of MC
from flexible urethane foam production.
73
-------
Process Description
In order to produce a foam, it is necessary to generate
nucleating bubbles within a gelling mixture. Polyurethane
elastoplastics are produced using either polyether polyols or
polyester and diisocyanates (combustion-retarding agents may also be
employed). These foams are available in pourable or injectable
liquid, preformed pelletized solids, and sheetstock. Flexible foams
are produced from polyether polyols, toluene diisocyanate (TDI), and
polymeric isocyanates.1 These foams are generally low-density, soft
foams that incorporate carbon dioxide gas as the primary blowing
agent.1 In the production of rigid polyurethane foam (made from
polyether polyols, combustion-retarding agents, polymeric isocyanates,
and low-boiling halocarbon blowing agents), MC is not used as a
blowing agent, but is often employed for filling and cleaning the
mixing head.
As mentioned previously, polyurethane foam production (especially
slabstock urethane foam) is the primary MC consumption source within
polyurethane foam-blowing production, and will be the focus of the
discussion in the following text.
Flexible polyurethane foam slabstock and flexible molded foam are
produced by the exothermic reaction of TDI with a polyol. As
mentioned, carbon dioxide is the primary blowing agent, with MC being
used as an auxiliary blowing agent. Production involves the mixing of
TDI and polyol directly with the blowing agents, catalysts (i.e.,
tertiary amines), foam stabilizers, and flame retardants.
The foam-producing reaction occurs within the "foam tunnel" of
the process production line. These foam tunnels are generally
conveyorized in-line systems enclosed on the sides by plastic
curtains. Chemical ingredients are normally pumped from tanks or
55-gallon drums to a mixing head and discharge nozzle.3 The nozzle
pumps the liquid reactants onto the conveyor belt within the tunnel.
An exothermic reaction of the chemicals produces the primary blowing
agent (e.g., carbon dioxide), which results from the reaction of
isocyanate with water, and vaporizes the secondary blowing agent
(e.g., MC), producing the foam cells during its formation. The heat
74
-------
evolved from the reaction of the isocyanate with the polyol and with
water is more than sufficient to boil or evaporate MC.
Foam slabs at varying dimensions reach their maximum height
within 4 minutes after the chemical liquid reactants are discharged
onto the conveyor. When this process involves the reaction mix being
poured into a closed mold, it produces a flexible polyurethane molded
foam.1 When such molds are not used, slabstock results.
Polymerization (e.g., gelling) reactions and further solidifying of
the foam occurs prior to the foam exiting the tunnel (an estimated
10 minutes). Following exit from the tunnel, the foam is further
cooled, prepared (e.g., sawed into slabs) and packaged.3
One of the most important processing parameters is temperature.
Temperature changes can affect the viscosity of the mixture, which
influences the pump's metering ability. Pumps are metered to enable
proper mixture composition, and differ according to whether high or
low pressure machines are used, or whether the process is done on a
batch or continuous basis.1 Figure 6 is a typical schematic flow
diagram of flexible polyurethane slabstock foam production that
illustrates the foam line tunnel conveyor and product preparation
steps .3
Emission Sources and Controls
The primary MC emission sources from polyurethane foam production
facilities include process vents, equipment leaks, and storage tanks.
Process vent emissions are primarily from vents above the foam
tunnel and in the foam curing area. Data obtained from a foam
manufacturer in 1986 included mass balance data that indicated that
approximately 60 percent of the initial MC charge is emitted in the
tunnel and approximately 40 percent is emitted in the curing area.3
Section 114 questionnaire responses from foam manufacturers reporting
the use of MC as an auxiliary blowing agent indicated that control
devices were not being used to reduce process vent emissions.3
Industry still reports that process vent controls are not employed
because of the expense; however, technological research on process
vent controls is underway.5 Industry also reports significant research
on process modifications to eliminate the use of MC in polyurethane
75
-------
ON
Flow Control
s .
Traversing Foam Hood
Exhausts to Atmosphere
J> Polyol ^>
S^ , Toluene ^s
/ Diisocyanate /
^> Water "/>
\ Blowing \
/ Agent /
(CFCorMC)
Surfactant J
? uatalysts ./
t i
-------
foam production.5 An emission factor for uncontrolled process vents
(foam tunnel, curing area) in the polyurethane foam (flexible
slabstock) production is presented in Table 20 .6 This emission factor
was derived on the assumption that MC consumption by the industry
equals process vent emissions, plus equipment leak and storage
emissions.3
Equipment leaks in polyurethane flexible foam production process
occur when the liquid or gas process stream leaks from components.
The following types of process components are used in foam production:
pumps, flanges, liquid valves, gas pressure relief devices, sampling
connections, and open-ended lines. As with MC production, the
methodologies outlined in the document, "Protocols for Generating
Unit-Specific Emission Estimates for Equipment Leaks of VOC and VHAP,"
can be used to estimate emissions from the production process
equipment leaks.7 An example of one of the simpler methods is
presented in Appendix A. An emission factor for uncontrolled MC
equipment leaks based on Section 114 questionnaire responses in 1985
is presented in Table 20 .6
Storage tank emissions can be derived by using EPA Publication
No. AP-42 factors with site-specific information.8 An example
calculation is presented in Appendix A. Accidental spills and
resulting emissions are considered to be minimal. An estimated
storage tank emission factor derived for uncontrolled storage tanks
(including fixed-roof tanks and pressurized tanks) using average
storage tank data from Section 114 questionnaire responses in 1985 is
presented in Table 20.s Facilities that have pressurized tanks were
assumed to have no emissions.
An aggregate emission factor for the entire production process is
also presented in Table 20,s and is based on the assumption that all
the MC consumed during the process is emitted to the air at some point
in the process.
Emissions Control--
Potential control techniques to reduce MC emissions from
polyurethane flexible foam production processes, and their estimated
control efficiencies are presented in Table 21.3
77
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TABLE 20. UNCONTROLLED EMISSION FACTORS FOR POLYURETHANE FOAM
PRODUCTION
Emission Factor
g/kg (Ib/ton) MC
Emission Source Consumed
Process vents (foam tunnel, curing area) 980 (1960)
Equipment leak emissions 17 (34)
Storage tank emission 3 (6)
Entire Process 1000 (2000)
Source: Reference 6.
78
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TABLE 21. CONTROL TECHNIQUES AND EFFICIENCIES USED TO ESTIMATE
CONTROLLED
EMISSIONS FROM POLYURETHANE FLEXIBLE FOAM PRODUCTION
Emission Source
Control Technique
Percent Reduction in
Methylene Chloride
Emissions
Process Vents:
Foam Tunnel
Curing Area
Storage Tanks
Equipment Leaks
Pump Seals
Packed
Mechanical
Valves
Gas
Liquid
Pressure Relief
Devices
Gas
Sample Connections
Open-Ended Lines
Foam Tunnel
Enclosure/ Carbon
Adsorption
None
Condenser
Monthly LDAR
Monthly LDAR
Monthly LDAR
Monthly LDAR
Rupture Disk
Closed Purge Sampling
Caps on Open Ends
95a
0
85
60-100b
60.8
60.8
73
59
100
100
100
Source: Reference 3.
a Assumes 100 percent capture efficiency within foam tunnel.
b Depends on control technique for given equipment component.
LDAR = Leak Detection and Repair
79
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As previously discussed, not all production facilities have been
located and contacted recently to discern whether controls are more
stringent now than in 1985. It is known, however, that MC use within
this industry has increased by 20 percent since 1984 as it has
increasingly been used as a substitute for CFC-11 in the production
process.
80
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REFERENCES FOR POLYURETHANE FOAM INDUSTRY
Occupational Safety and Health Administration Proposal for New
Methylene Chloride Standard, 56 FR 57045-57046, 57056-57057,
November 7, 1991.
"Chemical Proflie--Methylene Chloride," Chemical Marketing
Reporter, 241(9):42, March 2, 1992.
"Methylene Chloride Emissions from Flexible Slabstock
Polyurethane Foam Facilities," Memorandum from R. L. Ajax and S.
R. Wyatt, U.S. Environmental Protection Agency, Radian
Corporation, to J. Farmer, Standards Development Branch,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
April 21, 1986.
The Flexible Polyurethane Foam Handbook, Dow Chemical, Urethanes
Unlimited, 1985.
"Status of Control of Process Vent Emissions," Telephone
communication from Joanne O'Loughlin, Radian Corporation,
Research Triangle Park, NC, with H. Stone, General Foam
Corporation, West Hazelton, PA, April 20, 1992.
"Crosswalk/Air Toxic Emission Factor Data Base Management System
(XATEF), Version 1.2," Diskette, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1991.
Protocols for Generating Unit-Specific Emission Estimates for
Equipment Leaks of VOC and HAP, EPA-450/3-88-010.
U.S. Environmental Protection Agency, Research Triangle Park, NC,
October 1988.
"4.3 Storage of Organic Liquids," Compilation of Air Pollutant
Emission Factors, Volume I: Stationary Point and Area Sources,
Fourth Edition, AP-42, Chapter 12, Supplement E,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
September 1985.
81
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82
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PHARMACEUTICAL MANUFACTURING
The pharmaceutical manufacturing industry used approximately 11
percent of the total MC consumed in the United States in 1991.1
Methylene chloride is used in pharmaceutical manufacturing as a
general solvent, as an extraction solvent, and in tablet coatings.2'3
Although most of the MC is used in pill coatings, it is also used in
the manufacture of antibiotics, vitamins, contraceptives, and drugs
used to control hypertension and diabetes. Many facilities have been
able to reduce or eliminate MC from tablet coating operations and
substitute water or other safer chemicals. Previous EPA studies
indicate that there are over 800 pharmaceutical plants in the United
States and its territories,2 but MC is used in only 76 of these
facilities.4 Table 22 contains a partial list of pharmaceutical
manufacturing facilities that use MC. It should be noted, however,
that the information is based on a 1985 survey.3 A survey of 1989 TRIS
data revealed 74 pharmaceutical facilities using MC. Refer to
Appendix D for a list of these facilities. Ten of the facilities on
the TRIS list are found in Table 22.
Methylene chloride is useful in pharmaceutical extractions for a
number of reasons. Because of its low boiling point (40°C), it can be
used to extract heat-sensitive materials. It is useful in extractions
from water because it is immiscible with water, tends not to emulsify,
and has a high specific gravity (1.33 at 20°C) ,5'6 Some pharmaceutical
companies use MC as an extraction solvent because their product is
very soluble in MC.5
The main reason that MC is used to spray coating on tablets is
that it is highly volatile and so evaporates readily. Methylene
chloride is also useful if the tablet is sensitive to water and/or
heat.7 Methylene chloride forms a binary azeotrope with water (98.5%
by weight at 38°C) and can be used as a drying medium.5'6 This
azeotropic property can be important for coating crystals with another
water-soluble solid. A typical coating solution does not consist of
just MC, but is also composed of lesser percentages of alcohol and
solids. Methylene chloride is completely miscible with other
chlorinated solvents, diethyl ether, and ethanol, so the above mixture
can be varied to give the best coating.5'7 Some companies use MC
83
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TABLE 22. PARTIAL LIST OF PHARMACEUTICAL MANUFACTURING FACILITIES
THAT USE METHYLENE CHLORIDE
Facility
Location
Annual Capacity
kg/yr (Ib/yr)
Abbott Labs3
Aldrich Chemical
Beecham, Inc.3
Biocraft Labs3
Bristol-Myers3
Burroughs Wellcome3
Chemical Dynamics
Chemical Service
Ciba Geigy3
Deepwater, Inc.
Eli Lilly & Co.3
Frank Enterprises
Ganes Chemicals, Inc.
Genzyme
Henkel of America
Nepera, Inc.
Pfizer3
Squibb Corp.3
Upjohn3
(Fine Chemical Div)
Warner Lambert
William H. Rorer
Barceloneta, PR
North Chicago, IL
Milwaukee, WI
Piscataway, NJ
Waldwick, NJ
Syracuse, NY
Greenville, NC
S. Plainfield, NJ
West Chester, PA
Ardsley, NY
Summit, NJ
Compton, CA
Indianapolis, IN
Columbus, OH
Pennsville, NJ
Boston, MA
Kankakee, IL
Harriman, NY
Groton, CT
Terre Haute, IN
Kenly, NC
Arecibo, PR
Kalamazoo, MI
Holland, MI
Fort Washington, PA
2,300,000 (5,000,000)
b
270 (600)
45 (100)
b
b
45 (100)
b
b
b
b
b
b
b
10,000 (22,000!
b
b
b
Source: Reference 3.
3Also found in TRIS data.
bCapacity not available.
NOTE: These operating plants and locations were current as of
November 1985. The reader should verify the existence of
particular facilities by consulting current listings and/or
the plants themselves. The level of MC emissions from any
given facility is a function of variables such as capacity,
throughput, and control measures, and should be determined
through direct contact with plant personnel.
84
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because it dissolves cellulose acetate, which can be used for semi-
permeable membranes.5 Another reason for its prevalent use is that it
is easy to control emissions through activated carbon absorption, and
the MC retained can be reused without further purification.7
Even though MC has properties conducive to manufacturing
Pharmaceuticals, there has been an effort to reduce the amount used by
the industry because of possible negative health effects. Solvent
substitutes such as methanol and ethanol have been considered.
However, these substances are not always suitable because of
flammability and health concerns. Petroleum distillates and aqueous
solutions are being substituted for MC at some facilities.4'8
Pharmaceutical manufacturing operations are very diverse with some
plants using chemical synthesis to produce active ingredients
(fermentation and natural extraction are alternative means) and some
plants formulating final products (capsules, tablets, etc.).
Facilities may conduct one or more of the above operations.
Process Descriptions
Synthetic Organic Pharmaceutical Chemical Process--
Pharmaceuticals typically are manufactured in a series of batch
operations. The four successive stages of pharmaceutical production
include: chemical reaction, product separation, purification, and
drying. Figure 7 shows a typical batch synthesis operation.2 In the
chemical reaction stage, raw material solids and solvents such as MC
are mixed in a reactor vessel in which the chemical reaction is
carried out, sometimes under elevated temperature and pressure. The
stainless steel or glass-lined carbon steel reactor vessel is either
an open tank or an enclosed vessel, both equipped with an agitator.
Peripheral equipment such as condensers, a refrigeration unit, or a
vacuum system can be added to allow the reaction to take place at very
high or low temperatures and/or pressures. Some reactors are equipped
with a condenser for recirculation of the solvent.
After completion of the chemical reaction, the pharmaceutical
products are separated during the product separation stage. The
effluent is pumped from the reactor to a holding tank where the
reaction products are washed to remove unreacted raw materials and
85
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Vent
Solvent
(MC)
Solids
on
Vent
Vent
Reactor
H2M K2HT}
' ' Solvent
I I I Receiver
[-*• Solvent
J turn
(MC)
Tank
Solent
Dtetlttatlon
Crystallize
Reaction
Stage
Product
Separation
Stage
Purification
Stage
H2O
Solvent
(MC) Vent
Batch
Centrifuge
-if-
1H20
Solvent
(MC)
Vent
Dryer
Product
Drying
Stage
Source: Reference 2
Figure 7. Typical synthetic organic pharmaceutical chemical process.
i
i
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byproducts. The washed reaction products are then piped to various
separation process tanks. Product separation often utilizes an
extraction process in which a solvent (such as MC) preferentially
dissolves one of the reaction products.
Distillation, crystallization, and filtration are among the
purification techniques used after product separation or extraction.
Following product separation, the crude extracted product is purified
by crystallization of the desired compound from a supersaturated
solution. A filter press is usually used to separate the concentrate
from the solvent. The purified product and remaining solvent are then
separated in a centrifuge. The cake may be further washed with water
or another solvent to remove impurities before drying.
After the completion of the purification processes, products are
moved to dryers, such as tray, rotary, or fluidized bed dryers, which
use hot-air circulation or are operated under a vacuum to remove the
remaining solvents or water from the product.4
Tablet Coating Process--
Tablets are coated in rotating open-ended pans that range from
90 to 150 cm (36 to 60 inches) in diameter. The coating is sprayed on
the tablets in the pan while warm air (30°C) flows across the pan at a
typical rate of 28 cubic meters per minute (1000 cubic feet per
minute). The coating solution is made up of MC and alcohol (about
70/30) but water alone can be used.8 The air evaporates the solvents,
leaving coated tablets. Spray coating and drying takes 2 to 3 hours
per batch. A large plant might have 20 pans, whereas a small plant
might have only two. Any number of pans can be in use at any given
time. The pans are usually cleaned after each batch, even if multiple
batches of the same material are made.
Pharmaceutical products may also be coated by the Wurster
process. In this process, the tablets or pellets are suspended in a
fluidized bed while the spray solution is applied using a stream of
heated nitrogen.7'8 Methylene chloride is used as a solvent along with
alcohol (70/30) to dissolve the solids used to coat the tablets. This
solution is then sprayed on the cores, the solvents evaporated off,
and the vapors condensed and collected in a tank for reuse in the next
87
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batch.8 This method is used most often for coating pellets (smaller
particles that are later encapsulated), whereas coating pans are used
most often for coating tablets (standard dosages). A good example of
pellet coating would be over-the-counter 12-hour cold capsules.
Most tablets are coated with sugar, methyl cellulose, or ethyl
cellulose. Cellulose coatings may use either a water or an organic
solvent such as MC. Chloroform can be used in place of MC. The use
of water as a solvent or solvent component reduces VOC emissions, but
more time and heat are required to evaporate the water than for an
organic medium. Therefore, this is a production consideration. Also,
products that are sensitive to water and/or heat may preclude the use
of aqueous coatings. The use of heat or vacuum can expedite
evaporation, but this rapid evaporation can peel or roughen the
coating.
According to one manufacturer, the rotating pan units can process
batches between 400 and 800 kg (900 and 1,700 Ibs), with a total
yearly throughout between 192,000 and 363,000 kg (423,000 Ibs and
799,000 Ibs), of which 71,140 kg to 134,380 kg (156,510 Ibs to 295,630
Ibs) is product.8 Batch sizes using the Wurster process may vary, with
a minimum of 860 kg/batch (1,891 Ibs/batch) to a maximum of
3,787 kg/batch (8,331 Ibs/batch). In a year's time, a total of
112,820 kg (248,203 Ibs) of material were processed through the
Wurster column, of which 12,072 kg (26,558 Ibs) was product.8
Emission Sources
Pharmaceutical Chemical Synthesis--
Methylene chloride is released during storage, transfer,
reaction, separation, purification, and drying processes of
pharmaceutical chemical synthesis.4 Storage emissions result from
displacement of air containing the solvent during tank charging.
Chemical transfer operations, such as manually pouring solvent drum
contents, is a source of emissions. Reactor emissions result from the
displacement of air containing MC during reactor charging, solvent
evaporation during the reaction cycle, venting of uncondensed MC from
the overhead condenser during refluxing, purging of vaporized MC
following a solvent wash, and opening of reactors during the reaction
-------
cycle to take quality control samples. Distillation condensers can
emit MC as uncondensed solvent.
During crystallization, emissions can result from the venting of
vaporized solvent if the crystallization is being done by solvent
evaporation. If crystallization is accomplished by cooling of the
solution, there are few emissions. Dryers are potentially large
emission sources; emission rates vary during drying cycles, and with
the type of dryer being used. Emissions from air dryers are normally
greater than those from vacuum dryers mainly because air dryer
emissions are more dilute and difficult to control.2'4
Below is a ranking, in order of decreasing emissions, that
illustrates relative expected total VOC emissions from uncontrolled
pharmaceutical chemical synthesis process sources.2
• Dryers
• Reactors
• Distillation systems
• Storage and transfer systems
• Filters
• Extractors
• Centrifuges
• Crystallizers
For most pharmaceutical facilities, the first four listed process
sources will account for the great majority of total plant MC
emissions.2 In addition to the eight sources listed above, fugitive
emissions result from leaks in equipment components. The list differs
if controlled emissions are considered because emissions from reactors
and distillation systems can often be very efficiently condensed.
Tablet Coating--
Most emissions from tablet coating are process vent exhaust
emissions from pan tablet coating. Although the exhaust emissions are
often very dilute, they can be controlled with activated carbon
adsorption,7 which enables the manufacturing facility to recover the MC
89
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solvent. Emissions from tablet coating storage and transfer
operations, as well as fugitive emissions, are similar to those from
pharmaceutical chemical synthesis.
The Wurster process is operated as a totally closed system with a
solvent recovery system based on a refrigerated condenser maintained
at about 25°C, so emissions from this process are limited to
approximately 2 percent.8
Emissions Data and Controls
Emission Factors--
Surveys of drug manufacturers in 1975, 1982, and 1985 estimated
the final disposition of total MC usage. The responding firms were
estimated to represent approximately one-half of the production of
ethical (prescription) domestic Pharmaceuticals in those years. The
amount emitted into the air (instead of being incinerated, disposed of
into the sewer, etc.) varied from 43 to 67 percent of total MC
consumed.9"12 Table 23 illustrates the disposition of MC for all three
years.
Some emission factors were developed from 1985 process data
obtained from the Ciba-Geigy facility in Summit, New Jersey. This
information is summarized in Table 24.8 Emission factors for tablet
coating are shown both prior to control and after control by carbon
adsorption. No other current emissions data from pharmaceutical
manufacturing facilities were located.
As discussed previously in Section 4 for MC producers, site-
specific emissions estimates can be developed using the AP-42
methodologies for storage tanks, the "Protocols" methodologies for
equipment leaks, and the wastewater CTC document methodology for
wastewater. Example calculations are given in Appendix A.
Applicable Controls for Pharmaceutical Chemical Synthesis--
Applicable controls for the vented emissions mentioned earlier,
except storage and transfer, are: condensers, scrubbers, and carbon
adsorbers.2 Incinerators are not currently widely used to control
90
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TABLE 23. METHYLENE CHLORIDE PURCHASES AND ULTIMATE DISPOSITION BY PHARMACEUTICAL MANUFACTURERS
Ultimate Disposition (percent)
Year of
Data
1975
1982
1985
Annual
Purchase
(metric tons)
10,000a
ll,375b
1,539C
Air
Emissions
53
43
67
Sewer
5
5
8
Incineratio
n
20
38
4
Solid Waste
or Contract
Haul
22
11
10
Other
Disposal
--
3
7
Product
--
--
3
Source: References 9-12.
a Data represent 26 pharmaceutical manufacturers, which account for approximately 53% of 1975
domestic sales of ethical Pharmaceuticals.
b Data represent 17 pharmaceutical manufacturers, which account for approximately 50% of 1982
domestic sales of ethical Pharmaceuticals.
c Data represent 13 pharmaceutical manufacturers. Information concerning percentage of domestic
sales (as in 1975 and 1982 data) not available.
-------
TABLE 24. METHYLENE CHLORIDE EMISSION FACTORS
FOR PHARMACEUTICAL MANUFACTURING
Industrial
Process
Emission
Source
Emission Factor
Control Status
Pan tablet
coating
Blender
Coating
solution
holding tank
Process Vents
Process Vent
Process Vent
0.053 kg MC/kg product
0.001 kg MC/kg product
0.003 kg MC/kg active
ingredient processed
0.01 kg MC/kg coating
solution processed
Uncontrolled
Controlled
(dual carbon
bed adsorber)
Uncontrolled
Uncontrolled
Coating
solution
mixer
Process Vent 0.0001 kg MC/kg
coating solution
processed
Uncontrolled
Source: Reference 8.
NOTE: Emission data are for one facility only and do not represent
average emissions for all such sources, or total emissions
for all sources.
92
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vapor phase organic emissions from synthesized drug production
facilities.2 Part of the lack of use may be due to the variability of
waste gases that would be ducted to an incinerator and the batch
nature of the processes. Fluctuating flows and pollutant
concentrations may hamper safe and efficient operation. Therefore,
incinerators would most likely find application where relatively
stable waste gas flows can be established. Stability may be enhanced
by ducting emissions from several sources to a common control device.
It should be noted that incineration of MC results in hydrogen
chloride (HC1) , which is also an air pollutant.
Another potential disadvantage of using incinerators is that heat
recovery is likely to be uneconomical because at pharmaceutical plants
incinerators will be relatively small and the potential energy
recovery correspondingly small, especially when viewed in light of the
costs for installing heat recovery equipment.2 In addition, the
incinerator would generally run less than 24 hours a day. In this
case, heat recovery would be intermittent, thus decreasing its
utility.
Storage emissions can be controlled by storing MC in pressure
tanks or by venting storage emissions to a control device such as a
condenser, scrubber, carbon adsorber, or combustion device. Floating
roofs would be feasible controls for large, vertical storage tanks.2
These controls are the same as those applicable to emissions from
MC production. Transfer may be controlled by vapor balancing, where
MC vapors are returned to the storage tanks; or transfer emissions may
be vented to a control device.
Control of equipment leak emissions may be accomplished through a
regular inspection and maintenance program, as well as by equipment
modification. See Section 4 for more information regarding equipment
leaks.
Applicable Controls for Tablet Coating--
Figure 8 is a schematic of the pan tablet coating process solvent
recovery system.8 In this control method, the MC-contaminated air from
the dryer is passed through a bed of activated carbon (with control
efficiencies of 98+ percent). When the carbon bed becomes loaded with
93
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To Roof
Pan Exhaust
Solvent/Air
VO
Outside
Air
Tablet*
to
Accoto Cento
:O
Accela-
Coata
Coating Solution
Cooling Coil
Process Water
Air & Solvent from Stripper
Blower
Air & Solvent
Steam &
Carbon
Bed
I
Solvent
Vapors
Cooler
RM
Control
Carbon
Bed
dean
Steam
Ak to Roof
Light Layer
200 Gal
1.3% Solvent
In Water
Layer
To Drums
X
ChHted
Water
Primary
Secondary
Condenser
t*
I
X^X
X^^v
I
X^X
Process
Water
~* Chilled
_ Water
Sotvent
x^ ^v
^^^^fc^^J
Decanter
V^Heavy Layer
1
x_
Packed Bed
Ak Stripping Column
Alcohol & Water
SO ppm Solvent
Holding
Tank
Water &
Alcohol
To
Neutralization
or
Drums
Source: References
Figure 8. Pan tablet coating process solvent recovery system.
Outside Air
Blower
-------
organic compounds, it is stripped with low-pressure steam. Because MC
is insoluble in water, it is easy to separate from the steam
condensate for reuse. Any ethanol that is captured is miscible with
the steam condensate and is impractical to salvage. The condensate,
which contains 1-2 percent alcohol, is usually discarded to a sewer.
In a large pharmaceutical plant, this wastewater stream is processed
in the plant wastewater treatment system.7
Figure 9 describes the Wurster process solvent recovery system.8
With this system, about 98 percent of the solvents are recovered and
reused as is. Because there is no contact with water, no solvents
find their way to the sewer system.8 The remaining 2 percent of
solvents are presumably emitted into the air.
95
-------
V0
O*
Kern 1 Purged at End of Every Run
Balance of System as Required
for Maintenance
End of Run Vent
to Atmosphere
ReclrcuteUng Nitrogen
Source: References
1) Tablet Coating Column
2} Dust Collector
^x
3 } Condenser
^_x
4) Spent Solvent Reservoir
5) ReclrculallngFan
>•<
6) Heater
>-<
7) Coating Solution Tank
>-V
8j Coating Solution Pump
i
Figure 9. Wurster process solvent recovery system.
-------
REFERENCES FOR PHARMACEUTICAL MANUFACTURING
1. "Chemical Proflie--Methylene Chloride," Chemical Marketing
Reporter, 241(9):42, March 2, 1992.
2 . Control of Volatile Organic Emissions from Manufacture of
Synthesized Pharmaceutical Products, OAQPS Guideline Series, EPA-
450/2-78-029, U.S. Environmental Protection Agency, Research
Triangle Park, NC, December 1978.
3. "Telephone Survey of Pharmaceutical Manufacturing Industry,"
Memorandum from R. Nash, Radian Corporation, Research Triangle
Park, NC, to D. Beck, U.S. Environmental Protection Agency,
Research Triangle Park, NC, November 6, 1985.
4 . Occupational Safety and Health Administration Proposal for New
Methylene Chloride Standard, 56 FR 57048, 57060, November 7,
1991.
5. "Telephone and Literature Survey of Pharmaceutical Production,"
Memorandum from N. Cole, Radian Corporation, Research Triangle
Park, NC, to D. Beck, U.S. Environmental Protection Agency,
Research Triangle Park, NC, February 12, 1986.
6. Kirk-Othmer Encyclopedia of Chemical Technology, M. Grayson, ed.,
Volume 5, pp. 380, 686, 692. John Wiley & Sons, New York, NY.
1979.
7. Volatile Organic Compound Emission Controls for Tablet Coatings
at Pharmaceutical Plants, NTIS No. PB84-182922,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
January 1984.
8. Written communication from L. DellaVecchia, Ciba-Geigy Facility,
Summit, NJ, to Radian Corporation, Research Triangle Park, NC,
February 7, 1986.
9. Survey of Methylene Chloride Emission Sources, EPA-450/3-85-015.
U.S. Environmental Protection Agency, Research Triangle Park, NC,
June 1985.
10. Written communication from T. White, Pharmaceutical Manufacturers
Association, Research Triangle Park, NC, to D. Beck, U.S.
Environmental Protection Agency, Research Triangle Park, NC,
June 8, 1984.
11. Written communication from T. White, Pharmaceutical Manufacturers
Association, Research Triangle Park, NC, to D. Beck, U.S.
Environmental Protection Agency, Research Triangle Park, NC,
August 18, 1986.
12. "4.3 Storage of Organic Liquids," Compilation of Air Pollutant
Emission Factors: Volume 1, Stationary Point and Area Sources,
Fourth Edition, AP-42, Chapter 12, Supplement E, U.S.
Environmental Protection Agency, Research Triangle Park, NC,
September 1985.
97
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SOLVENT CLEANING AND PHOTORESIST STRIPPING
An estimated 11 percent (16,420 Mg) of total 1991 United States MC
consumption was used for metal cleaning (also called degreasing) in a variety
of manufacturing processes, and 3 percent (3,400 Mg) was used for photoresist
stripping in printed circuit board manufacture in the electronics industry.1'2
Solvent cleaning is a process used to remove water-insoluble soils from
metal, plastic, fiberglass, printed circuit boards, and other surfaces.
Water-insoluble soils include grease, oil, waxes, carbon deposits, fluxes,
tars, metal chips, mold-release agents, and oxidation layers. Solvent
cleaning is used by a variety of industries that employ cleaning processes as
part of their manufacturing process or prior to painting, plating, inspection,
repair, assembly, heat treatment, and machining. Typical industries that use
solvent cleaning processes include furniture and fixtures, fabricated metal
production, electric and electronic equipment, transportation equipment,
plumbing fixtures, aerospace manufacturing, miscellaneous manufacturing,
primary metals, automobile and electric tool repair shops, and railroad, bus,
aircraft, and truck maintenance facilities.3 Because of the large number of
solvent cleaning operations existing within many different industries,
information on the location of the individual solvent cleaning equipment is
difficult to obtain. The following sections discuss the solvent cleaning
industry, cleaning process descriptions, and emissions.
Process Descriptions
Solvent cleaning processes are typically performed by two basic types of
solvent cleaning equipment: batch cleaners and in-line cleaners (also called
continuous cleaners). Both cleaners exist in designs for use with solvent at
room temperature (cold cleaners) or solvent vapor (vapor cleaners). Methylene
chloride solvent cleaning processes for each solvent cleaner [e.g., batch
vapor cleaners, in-line cleaners (cold and vapor), and batch cold cleaners]
are discussed in the following sections.
99
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Batch Vapor Cleaner Process Description--
Batch vapor cleaners heat solvent to a boiling point, creating a solvent
vapor zone into which items to be cleaned are lowered. The cleaning process
involves the solvent vapor condensing on the item and stripping soils away.
Cleaning can also be supplemented or replaced by immersing items into the
liquid solvent during the cleaning cycle. Batch vapor cleaners include open-
top vapor cleaners (OTVC), and non-OTVC batch cleaners developed with design
variations to meet particular workload characteristics and cleaning demands
for particular applications.3
Open-top vapor cleaner and non-OTVC batch cleaners are designed to
generate and contain solvent vapor. The basic OTVC batch cleaner is
illustrated in Figure 10. It is equipped with a heating system or pump to
boil liquid solvent. As the solvent boils, dense solvent vapors rise to the
level of the primary condensing coils. The primary condensing coils circulate
coolant (e.g., water, refrigerant) through the coils, providing continuous
condensation of the rising solvent vapors and creating a controlled vapor zone
that prevents most vapor from escaping the tank. Solvent vapor and moisture
in the air collect in a condensate trough along the sides of the OTVC below
the primary condensing coils. This condensate goes into a water separator.
The water separator is a container that separates the water from the liquid
solvent, returning solvent to the cleaner and routing water for use in another
process within the facility/plant or to disposal to a publicly owned treatment
works (POTW) system. Some batch OTVC cleaners may also use a canister of
desiccant to replace or aid the water separator in its reduction of water
contamination. The OTVC walls also extend above the top of the vapor zone.
This area is called the freeboard. A freeboard reduces air currents and
disturbance of the vapor zone boundary.3
Design variations of OTVC batch cleaners are numerous, and depend on the
particular characteristics and demands of the workload. Examples of design
variations incorporated in OTVC batch cleaners include stills, lip or slot
exhausts, covers, and multiple-chamber cleaners. Stills are used to extract
soils from the solvent sump and return clean solvent to the machine,
decreasing the need to replace the cleaning solvent because of impurities.
Lip or slot exhausts are designed to capture solvent vapors escaping from the
OTVC and carry them away from the work area, and are incorporated to reduce
occupational exposure. Covers, in varying designs, are used to limit solvent
losses and contamination during downtime or idling time. Multiple-chamber
design variations can include various solvent-cleaning methods (e.g., vapor,
immersion, spraying).3
100
-------
Primary
Condensing Coils
Temperature
Indicator
Cleanout Door
Freeboard
Refrigeration
Device
Solvent Level Sight Glass
Freeboard
Condensate Trough
Water
Separator
Heating. Elements
Work Rest and Protective Grate
Source: Referenced
Figure 10. Open top vapor cleaner.
IN
CO
to
101
-------
There are some batch vapor cleaners that are not OTVCs. These include
cleaners into which a batch of parts is loaded, and then moved through the
cleaner on a conveyor (called a conveyorized batch cleaner) and batch cleaners
that are more enclosed than OTVCs. These batch vapor cleaners tend to be
larger than the OTVC batch cleaners and employ similar cleaning methods (e.g.,
condensing vapor, immersion, spray). These cleaners are a hybrid of an OTVC
and continuous cleaner. Examples include cross-rod, vibra, ferris wheel, and
carousel cleaners. An example of a cross-rod, non-OTVC batch vapor cleaner is
illustrated in Figure II.3
The cleaning process for OTVC and non-OTVC batch cleaners entails
solvent vapors condensing on the cooler workload entering the vapor zone until
the workload temperature approaches the temperature of the vapor. The
condensing solvent dissolves and flushes soils from the workload until
condensation ceases and the vapor-phase cleaning process is complete. As
discussed previously, the vapor cleaning process can also include immersion of
the item to be cleaned into the hot, liquid solvent.
Immersion batch vapor cleaning processes often include the use of
ultrasonics. Ultrasonics uses high-frequency sound waves that produce
pressure waves in the liquid solvent. The areas of low pressure within the
solvent form small vapor pockets that collapse as the pressure in the zone
cycles to high pressure. The creation and collapse of these vapor pockets
aids in cleaning by providing a scrubbing action.
Because of their higher boiling points, impurities (e.g., grease, soil,
wax, etc.) from the cleaning process minimally contaminate the solvent vapors.
Solvent can be used in vapor cleaning for a longer time than in cold cleaning
because of the affinity of the solvent vapor to remain relatively pure as
compared to immersion cold cleaner solvent. Another variation in the cleaning
process is the use of spray solvent below the vapor line. The pressure of the
spray and/or the potential for solvent condensation on the workload aids in
the physical cleaning of the workload.
102
-------
Conveyor
Path
Supports
Work /
Basket'
Water
Jacket
Boiling Chamber
Source: Reference 3
Figure 11. Cross-rod cleaner.
O)
m
-------
In-Line (Vapor and Nonvapor) Cleaner Process Description--
In-line cleaners (also known as continuous cleaners) are cleaners that
use automated loading on a continuous basis. The same cleaning techniques are
employed in in-line vapor cleaners as with batch vapor cleaners. In-line
nonvapor cleaning involves the use of solvent at room temperature, where
immersion and spray cleaning techniques can be employed. Most of these
cleaners, however, operate as vapor cleaners.3
In-line cleaners are usually enclosed, except at the inlet and exit
openings where the parts and conveyance pass. They also are typically
employed in industries that demand a larger-scale cleaning operation. Design
variations within these cleaners are determined by the workload and production
rate required. In-line cleaners include monorail, belt, strip, printed
circuit board processing equipment (i.e., photoresist strippers, flux
cleaners, and developers), and modified cross-rod non-OTVC batch cleaners with
both an entry and exit port. An example of a monorail in-line cleaner is
illustrated in Figure 12.3
Photoresist stripping processes involve using MC to remove any unwanted
resist from printed circuit boards. In 1989, 68 percent of MC reported for
use in the electronics industry was used in photoresist stripping.3 Assuming
this percentage remained the same for 1991, an estimated 3,400 Mg would have
been consumed for use in photoresist operations in 1991.l'2 A diagram of an
in-line photoresist stripping machine is illustrated in Figure 13.3
Batch Cold Cleaner Process Description--
Cold cleaners are usually used in small cleaning solvent maintenance
demand situations. The solvent cold cleaning process involves the use of the
solvent at room temperature. Cleaning is accomplished by spraying, flushing,
wipe cleaning, agitating, or immersing of item to be cleaned with the solvent.
104
-------
Conveyor
Path
Conveyor .
Path Spray
Pump
Boiling
Chamber
Water
Jacket
Source: Referenced
Figure 12. Monorail in-line cleaner.
3
<*)
(N
00
-------
o
Ov
Work Flow
Exhaust
Spray
Nozzles
Exhaust Damper
Water Rinse
A A A
Solvent
8 fr
Hill
Pump
n-i
^^ ^N ^N
P §-
Conveyor
Rollers
o o o
TJ 5" o
Drying
Area
Clean Solvent
(from Distillation
System)
, To Wastewater
Treatment System
Source: Reference 3
Figure 13. Schematic diagram of an in-line photoresist stripping machine.
CE
00
o
-------
The only known machine specifically manufactured for cold cleaning
purposes (except for non-vapor in-line cleaners) are carburetor cleaners used
in automobile repair operations. Methylene chloride is used in these cleaners
to increase the soil dissolving power and reduce the flammability potential of
the solvent cleaning blend employed. An example of a carburetor cold cleaner
is illustrated in Figure 14.3
Emissions Sources
Methylene chloride emissions from organic solvent cleaners are
air/solvent vapor interface emissions and workload-related emissions.
Air/solvent vapor interface emissions that result during idling conditions
(when a machine is turned on and ready to operate) are from solvent vapor
diffusion and convection. Workload-related emissions result from the
introduction and extraction of items cleaned during the cleaning process and
spraying processes (if employed) including emissions that occur by solvent
carry-out on the workload. Other solvent emission sources include leaks from
cleaners or associated equipment, filling and draining operations, and
startup, shutdown, and downtime operations.3
Idling Solvent Vapor Emissions--
Air/solvent vapor interface emissions under idling conditions in OTVC
batch cleaners result mainly from the diffusion of solvent vapors from the
vapor zone to the ambient air. Convection losses occur when the heat of a
boiling solvent is translated to the solvent cleaner walls, creating a
convective upward flow of solvent vapor to the outside of the cleaner. When
air flow is introduced across the air/solvent vapor interface because of draft
or lip exhaust, the diffusion rate and convection of solvent vapor to ambient
air increases. Figure 15 illustrates batch cleaner idling emission sources.3
In-line and non-OTVC batch cleaner idling air/solvent vapor loss
mechanisms are the same as for OTVC batch cleaners (e.g., diffusion,
convection). Figure 16 illustrates these emission sources for an in-line
cleaner. The solvent emissions from in-line and non-OTVC cleaners are
expected to be less than from OTVC cleaners because these cleaners are more
enclosed and therefore less exposed to drafts and their associated air/solvent
vapor emissions.3
Cold cleaner air/solvent vapor emissions under idling conditions occur
from evaporation and diffusion. The only known, manufactured cold cleaner is
a carburetor cleaner that generally uses MC with an overlaying water layer
(MC is heavier than water), so minimal solvent is expected to evaporate.3
107
-------
Air Motor and
Drive Assembly
Basket
"On" and "Off"
Valve
Source: References
Figure 14. Carburetor cleaner.
$
108
-------
/
Retractable
Cover
Water
Separator
Air Currents from
Building Ventilation
m
le
1 - - 7- -^
1 I 1 S*\ Freeboard \ ( 1 )
1 ' CU Area 1 , >j \
1 1 / ' ' \ ^p /|l
^ ^
oj Solvent
Zo
1 NT^-i
Vapor \ |o
*e Air/Solvent Interface
— •„ ~ "~^~.— ~~ —
— __; Boiling Solvent —
4
^~
1. Diffusion of Solvent from Air/Solvent Vapor Interface
2. Convection of Solvent Vapor up Warm Tank Walls
3. Diffusion and Convection Emissions Accelerated by Drafts
Across Tank Up (or by Operation of Up Exhaust Device)
Primary Condenser
Coils
Source: References
cc
in
Figure 15. Batch cleaner idling emission sources.
O)
CO
-------
Parts
Basket
Exhaust
Exhaust
-§--^ L-
Source: Reference 3
1. Diffusion of solvent from air/solvent vapor interface
2. Vapor up warm tank walls
3. Carry-out of liquid solvent on part and subsequent evaporation
4. Roof vent exhaust
Figure 16. In-line cleaner emission sources.
Sf.
CM
§
CM
O
-------
Workload-Related Solvent Vapor Emissions--
Workload-related solvent losses from OTVC batch cleaners are due to the
turbulence and vapor line fluctuation that occur at the air/solvent vapor
interface when items to be cleaned enter and exit the vapor zone. Turbulence
occurs when the items to be cleaned enter the cleaner. Emissions are
influenced by the means of conveyance (e.g., manual or automated). Emissions
occur from diffusion and convection, and increase with the speed of transfer
of the items into and out of the cleaner.3 An automated hoist system set at a
fairly low and even speed can reduce both in-plant and atmospheric emissions
(when emissions are vented to the atmosphere) by reducing the disturbance of
the air/solvent vapor interface.
Solvent loss from work-load-related conditions also occurs when solvent
spray cleaning is employed. Solvent spray cleaning causes turbulence in the
air/solvent vapor interface. Pooled liquid solvent and residual solvent film
remaining on the items cleaned after removal from a cleaner can also be a
source of solvent emissions to the air. These are called carry-out losses.
If a longer dwell time (i.e., length of time the part remains in the vapor
zone)4 and parts orientation to facilitate drainage of pooled solvent is
incorporated, liquid solvent carry-out emissions can be decreased.3 Simple
working practices, such as increasing the part dwell time and parts
orientation considerations may offer significant emission reductions (reducing
in-plant and atmospheric emissions).
In-line and non-OTVC batch cleaner workload-related solvent vapor
emissions are similar to emissions from OTVC batch cleaners. Workload-related
emissions from these cleaners, however, are less on a per-part basis than
those from manually operated OTVCs. Turbulence at the air/solvent vapor
interface (or the air/solvent interface for in-line cold cleaners) is less for
these cleaners than for the manually operated OTVCs because of the automation
and associated speed control of parts through the cleaning process. Exhaust
systems in these cleaners, unless controlled by a carbon adsorber, can result
in significant solvent emissions since air movement by exhaust systems may
increase diffusion and convection emissions.3 It is important to note that
although exhaust systems may decrease worker exposure in-plant, there is an
associated increase in emissions to the atmosphere.
Workload-related solvent emissions from cold cleaners result from
solvent agitation and spraying, and solvent liquid and film carry-out.
Efforts to facilitate drainage (i.e., tipping of parts, longer drainage time)
decrease solvent carry-out emissions.3
Ill
-------
Other Emission Sources--
Other solvent emissions sources include storage and handling operations,
startup, shutdown, and downtime operations, leaks, wastewater, filling and
draining operations, distillation operations, and solvent decomposition.
These losses will depend on the cleaning machine integrity and design, and the
operating techniques employed. Emissions for storage, leaks, and handling
losses from the solvent cleaning industry can be estimated by the same
methodology as discussed for the MC production industry in Section 4.
Appendix A presents an example of simple calculations for fixed-roof storage
tanks and equipment leaks; but as described in Section 4, there are also other
methods of emission estimation available for equipment leaks and other storage
tank configurations. Particular facilities and processes will require
differing factors, and reference to EPA Publication No. AP-42 for storage and
the "protocols" document for equipment leaks is suggested.
Emission Controls
Solvent control strategies involve machine design and operating
practices to minimize emissions from the sources discussed. Available control
techniques (including hardware and operating practices) for batch OTVC, in-
line (vapor and nonvapor), and cold cleaner operations are shown in Tables 25,
26, and 27, respectively. The EPA published a control techniques guideline
(CTG) document for solvent metal cleaning in 1977, and an alternative control
technology document for halogenated solvent cleaners in 1989. Thirty-three
States and the District of Columbia adopted the CTG-based RACT for solvent
cleaning emission.
The CTG developed two levels of control (A and B). Control System A
specified simple control equipment (e.g., covers and implementation of good
operating practices), and System B required that there be other control
equipment (i.e., freeboard extension, freeboard refrigeration device)
installed in addition to the System A controls.3 Presently, a proposal for a
National Emission Standard for Hazardous Air Pollutants (NESHAP) for the
control of halogenated solvent emissions from cleaners is being developed, and
a regulation and supporting document is scheduled to be finalized in 1994.
112
-------
TABLE 25. AVAILABLE CONTROL TECHNIQUES FOR OTVC OPERATIONS
Source of
Solvent
Loss
Available Control Hardware
Operating Practices
Air/Solvent
Vapor
Interface
Workload
Fugitive
1.0 freeboard ratio (FBR) (or
higher)
Freeboard refrigeration device
Reduced primary condenser
temperature
Automated Cover
Enclosed design
Carbon adsorber
Reduced air/solvent vapor interface
area
Automated parts handling at
3.4 meters per minute (11 fpm) or
less
Carbon adsorber
Hot vapor recycle/superheated vapor
system
Sump cooling system for downtime
Downtime cover
Closed piping for solvent and waste
solvent transfers
Leakproof connections; proper
materials of construction for
machine parts and gaskets
Place machine where there are no
drafts
Close cover during idle periods
Rack parts so that solvent drains
properly
Conduct spraying at a downward
angle and within the vapor zone
Keep workload in vapor zone until
condensation ceases
Allow parts to dry within machine
freeboard area before removal
Routine leak inspection and
maintenance
Close cover during downtime
Source: Reference 3.
-------
TABLE 26. AVAILABLE CONTROL TECHNIQUES FOR IN-LINE OPERATIONS
Source of
Solvent
Loss
Machine Design
Operating Practices
Air/Solvent
Vapor
Jnterface
Workload
Fugitive
1.0 freeboard ratio
Freeboard refrigeration device3
Reduced primary condenser
temperature3
Carbon adsorber
Minimized openings (clearance
between parts and edge of machine
opening is less than 10 cm or 10%
of the width of the opening)
Conveyor speed at 3.4 meters per
minute (11 fpm) or less
Carbon adsorber
Hot vapor recycle/superheated vapor
system
Sump cooling system for downtime
Downtime cover or flaps
Closed piping for solvent and waste
solvent transfers
Leakproof connections; proper
materials of construction for
machine parts and gaskets
Rack parts so that solvent drains
properly
Conduct spraying at a downward
angle and within the vapor zone3
Keep workload in vapor zone until
condensation ceases
Allow parts to dry within machine
before removal
Routine leak inspection and
maintenance
Close ports during downtime
Source: Reference 3.
a Applies to in-line vapor cleaners, but not in-line cold cleaners.
b Air/solvent interface for in-line cold cleaners.
-------
TABLE 27. AVAILABLE CONTROL TECHNIQUES FOR COLD CLEANERS
Machine Design Operating Practices
• Manual Cover • Close machine during idling and downtime
• Water cover with internal baffles • Drain cleaned parts for at least
15 seconds before removal
• Drainage facility (internal) • Conduct spraying only within the confines
of the cleaner
i-1 ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^=^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^=
i-1
171 Source: Reference 3 .
-------
Emission Estimates
Solvent usage and emission factors for uncontrolled and controlled
cleaners are shown in Table 28.4/5 In this table, the uncontrolled emission
factors are expressed in two ways. The factors on the first line are
expressed in terms of MC emitted per total MC used in the cleaning operation.
(The fraction not emitted is contained in waste solvent.) These factors may
be more representative for estimating emissions from an individual facility
that has information on the total MC it purchased (or consumed) for cleaning,
regardless of whether that MC was fresh (virgin) solvent from an MC production
plant or MC recovered from waste solvent and re-sold by a solvent recycling
company.
The second line of factors were developed for estimating emissions from
national data on how much fresh MC produced by MC producers was used for
solvent cleaning. These factors are expressed in terms of emissions per kg of
fresh MC used (see footnote "c").
National baseline emissions calculated using these emission factors are
presented in Table 29.4 These estimates take into account regulated and non-
regulated counties in the United States. To estimate emissions, solvent usage
for unregulated counties was multiplied by an emission factor that represented
116
-------
TABLE 28. METHYLENE CHLORIDE USAGE AND EMISSION FACTORS FOR UNCONTROLLED AND CONTROLLED CLEANERS
Parameter
Cold Cleaners
Carburetor
Cleaners9
OTVCs
In-line
vapor cleaners
Photoresist
strippers
Emissions Parameter
Uncontrolled EF w/o recycle
[kg emitted/kg total solvent used (fresh and
recycled)]b
Uncontrolled EF w/recycle
(kg emit ted/kg fresh solvent used) c'd
0.66
0.66
0.78
0.85
0.70
CTG Control System B efficiency (%)
Controlled EF w/recycle
(kg emitted/kg fresh solvent
used)c-a
Relative controlled fresh solvent usage (%)e
17
0
0
.0
.87
.85
60
0
0
.0
.76
.47
40
0
0
.0
.89
.63
60
0
0
.0
.91
.43
60
0
0
.0
.78
.46
Sources: References 4 and 5.
a It is assumed that all carburetor cleaners are controlled at baseline, so only the controlled emission
factor is used in calculations.
b This is the amount emitted by a cleaner per kg of total solvent (MC purchased for cleaning (includes virgin
fresh solvent plus solvent bought from recycling companies).
Emission factors are expressed on a fresh solvent (MC) feed basis.
MC used.
The units are kg emitted per kg fresh
d The term "recycle" refers to the information that, on a national basis, 75 percent of the MC contained in
waste solvent streams is recovered by recycling companies and resold for further use in cleaning. This
results in a reduction in the amount of fresh solvent required for a given cleaning application, but the
percentage of fresh solvent usage that is ultimately emitted by the cleaning process is higher. See
Appendix E for calculations and assumptions made for uncontrolled emission factor with recycle.
e The relative controlled solvent usage is defined as the amount of fresh solvent used by an uncontrolled
cleaner to perform a given cleaning job.
EF = Emission Factor
-------
TABLE 2 9.
(1987)d
NATIONAL EMISSIONS OF MC FROM ORGANIC SOLVENT CLEANERS,
Emissions (Mg/yr)
Type of Cleaner
Cold Cleaner
Carburetor Cleaner
Photoresist Stripper
OTVC
In-Line Vapor Cleaner
Uncontrolled
Cleaners3
9,
6,
3,
1,
300
0
540
230
370
Controlled
Cleanersb
1,
1,
1,
1,
480
620
110
490
430
Total
10
1
7,
4
1
, 800
,620
650C
,720
,800
Source: Reference 4.
a Refer to cleaners that are uncontrolled at baseline.
b Refers to cleaners assumed to be controlled with CTG Control System B
at baseline.
c This includes baseline emissions at 755 Mg/yr reported by nine large
photoresist stripping operations responding to EPA questionnaires in
addition to emissions of 6,890 Mg/yr calculated using the approach
described in this section.
d It is important to note that these emission estimates are based on
1983 solvent cleaning consumption estimates for fresh MC. Regulatory
activity affecting the use of MC in recent years has resulted in
fluctuations and decline in the use of MC. Methylene chloride 1991
consumption estimates for the solvent cleaning industry have been
reduced 48 percent when compared with the consumption estimates that
were used to calculate the emissions presented in Table 29.1/3'4
However, it is not possible to apply this percent consumption
decrease directly to scale down the 1983 national emission estimates
to produce 1991 estimates, because other factors, such as county
MC usage patterns and the distribution of controlled versus
uncontrolled cleaners, have changed over time. These changes would
need to be quantified to estimate emissions from current consumption.
118
-------
uncontrolled solvent cleaners, and solvent usage for regulated counties was
multiplied by an emission factor that represented controlled solvent cleaners.
119
-------
REFERENCES FOR SOLVENT CLEANING AND PHOTORESIST STRIPPING
1. "Chemical Profile--Methylene Chloride," Chemical Marketing Reporter,
241(9):42, March 2, 1992.
2. "Solvent Use in Electronics--1989," Memorandum from Steve Risotto,
Center for Emission Control, HSIA, Washington, DC, to Chris Sarsony,
Radian Corporation, Research Triangle Park, NC, April 2, 1992.
3. Alternative Control Technology Document - Halogenated Solvent Cleaners,
EPA-450/3-89-030, U.S. Environmental Protection Agency, Research
Triangle Park, NC, August 1989.
4. "Calculation of Number of Organic Solvent Cleaners and Solvent Emissions
and Use Per Model Plant," Memorandum from R.C. Mead and R.F. Pandullo,
Radian Corporation, Research Triangle Park, NC, to D. Beck,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
September 8, 1987.
5. "Documentation of Emissions and Long-Term Exposure Model Inputs for the
Organic Solvent Cleaning Source Category," Memorandum from R.C. Mead and
R.F. Pandullo, Radian Corporation, Research Triangle Park, NC, to
D. Beck, U.S. Environmental Protection Agency, Research Triangle Park,
NC, September 3, 1987.
120
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AEROSOL PACKAGING AND DISPENSING
An aerosol is a suspension of solids or liquid particles in a gas that
consists of a liquid and vapor phase. The liquid phase comprises active
ingredients, solvent, and liquefied propellant or co-solvent. The vapor phase
consists of the propellant that provides the positive pressure to expel the
contents of the container.1
In an aerosol dispensing system, a liquid propellant keeps the pressure
in the container constant as the product is being consumed. Methylene
chloride is used in the aerosol industry as a solvent, co-solvent, and vapor
pressure suppressor.2 A solvent with the properties of MC acts to bring the
active ingredient into solution with the propellant. A co-solvent is often
used with MC when it is desirable to also have another liquid that is not
miscible with the propellant (e.g., water). Methylene chloride, because of
its high vapor pressure, high boiling point, formulation compatibility, and
ability to depress the vapor pressure of high-pressure propellants, decreases
the flammability of the formulation mixture and enhances dispersion of the
aerosol spray.
Use of MC in aerosols has decreased because of Federal government
labeling requirements on consumer goods containing potential carcinogens, such
as MC. Substitutes for MC in aerosols with diversified uses include
1,1,1-trichloroethane (TCA), tetrachloroethane, mineral spirits, and water-
soluble formulas.3 Substitutes with limited uses include 1,1,2-trichloro-
1,2,2,-trifluoroethane.3
Air emissions of MC result from packaging and consumer use of aerosols.
The following sections discuss the aerosol packaging industry, aerosol
packaging and dispensing processes, emission sources, and emission estimates
of MC from aerosol packaging and use.
Aerosol Packaging Industry
There are an estimated 212 aerosol packaging companies, which consumed
an estimated 8 percent (10,000 Mg) of the 1991 MC production.4-5 The U.S. MC
demand for use in aerosol products has decreased steadily in recent years
because of environmental and occupational health concerns.5 In 1987, aerosol
121
-------
products containing MC reported by aerosol packaging companies included
insecticides, cleaners, lubricants, spot removers, paints, primers, adhesives,
sealants, enamels, and mold releases.6 Since 1987, however, there has been a
trend away from the use of MC toward the use of TCA in aerosol products. The
U.S. production of TCA, however, is being phased out under the Montreal
Protocol and the 1990 amendments to the Clean Air Act, as TCA is considered an
ozone depleting substance. There has been a corresponding trend back toward
the use of MC.7 Solvent TCA production levels will be cut incrementally until
phase-out at the end of the decade, and buyers are subject to an escalating
excise tax to discourage use. Increasing pressure to find other solvent
substitutes for MC is being exerted by the new OSHA-proposed MC exposure
standard discussed in Section 3.3
Industry reports that the product types and range of MC content within
the aerosol products reported in 1987 are similar to the MC content range
within aerosol products today, but that the number of products, and volume of
MC consumed by the aerosol industry has been dramatically reduced.7
Consumption reduction of MC by the aerosol industry since 1987 is exhibited by
Chemical Marketing Reports Chemical Profile of MC in 1991, which estimates a
49 percent reduction in aerosol consumption from 1988 (19,600 Mg/yr) to 1991
(10,000 Mg/yr).5-8 A national list of 212 aerosol packagers that have the
potential to consume chlorinated solvents was developed by the EPA in 1987.
Appendix C includes the names, locations, and product types packaged at these
facilities when data were available.4
Section 114 questionnaires containing questions about MC and other
chlorinated solvent emission sources and methods of recovery or control were
distributed to nine aerosol packaging companies. Eight of the nine companies'
questionnaire responses (containing information on 11 facilities) were
analyzed. Table 30 contains a list of aerosol product types reported in the
Section 114 questionnaire responses and information on the amount of
chlorinated solvent reported for each product type.4
122
-------
TABLE 30. WEIGHT PERCENT OF METHYLENE CHLORIDE IN AEROSOL PRODUCT TANKS,
REPORTED BY SECTION 114 QUESTIONNAIRE RESPONDENTS (1987)
Methylene Chloride
Product Type Meana Range13
Spray Paints0 27 5-40
Insecticides 19 10-42
Lubricants'3 17 5-55
Cleaners6 26 5-50
Adhesives 37 5-50
Paint Strippers 80 75-85
Source: Reference 4.
a The eight Section 114 questionnaire recipients were asked to provide the
typical concentrations (weight percent) of chlorinated solvent in each
product type. The value is the value of the reported typical
concentrations.
b The range of typical concentrations reported by the eight questionnaire
respondents.
c Includes enamels, coatings, primers, and rust inhibitors.
d Includes mold release agents and metal cutting fluids.
e Includes solvent degreasing cleaners, automotive, household, and electrical
contact cleaners.
123
-------
Process Description
Aerosol Packaging--
Aerosol packaging processes are batch-mode operations. Many companies
contract out aerosol packaging because of high plant costs. Some companies
fill other companies' products as well as their own, while others only fill
aerosols for other companies.3 Methylene chloride is generally supplied by an
outside chemical supplier, who delivers the solvent either by a tank truck or
by drums. Storage of MC can be in fixed-roof or pressurized tanks, or in the
drums (normally 55-gallon drums) in which the solvent was delivered.4
The initial stage of the aerosol packaging process involves the mixing
of the aerosol product ingredients in mixing tanks of varying sizes.
Ingredients, including MC, are either pumped from storage tanks or are poured
directly from storage drums. Ingredients are added according to volume or
weight. In order to minimize solvent loss due to volatilization, some
facilities add the solvent directly to the aerosol cans at the time of filling
rather than adding the solvent at the mixing tank stage. Mixing tank
ingredients, after being properly mixed, are either pumped or transported to
the aerosol can filling lines.4
Aerosol can filling involves filling with product, inserting the valve
stem and valve, adding propellant, and sealing the product in the can. Empty
aerosol cans are conveyed to an automatic filler that uses filling nozzles to
deliver the product into the empty cans. Filled aerosol cans are then
conveyed to a point where the valve stems and valves are inserted into the
can. The cans, still unsealed, are conveyed to a special "explosion-proof"
room where the propellant is added to the cans. The cans are then sealed
under pressure and conveyed to a point at which actuators are placed onto the
stems. To complete the aerosol packaging process, each can is weighed to
ensure weight requirements are met, submerged in a hot bath to check for
leaks, and washed, labeled, capped, and packaged according to the particular
requirements of the product.4 An example of a typical aerosol spray system is
illustrated in Figure 17.9
124
-------
Actuator
Valve
Container
Aerosol Spray
(Pressure
approx 35 pslg
at70*F)
Solution of Propellent
and Product
Source: References
Figure 17. Typical aerosol spray system.
125
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Aerosol Dispensing--
As illustrated in Figure 17, the aerosol spray dispensing product
comprises of four basic components: propellant, product, container, and
valve. A propellant is defined by the Department of Transportation as "a
material which can expel the contents of an aerosol container at room
temperature."3 Propellants typically are liquefied gases with vapor pressures
greater than atmospheric pressure, which enables product contents to be forced
from the container when the valve is activated at room temperature. The
product contains the solvent, co-solvent, and active ingredients that, in
conjunction with the propellant, enable the product to perform its desired end
function.
The dispensing process of an aerosol spray is achieved by depressing the
actuator, which causes depression of the valve, releasing a solution of
propellant and product to the air. The pressurized container allows
propellants that are gaseous at atmospheric pressure to exist predominantly as
a liquid. As the propellant is released, it converts to gas phase and
disperses the product. Some gas-phase propellant remains in the container
head space, while the rest is in equilibrium with the product. Examples of
propellants used in aerosol dispensing systems include hydrocarbons, dimethyl
ether (DME), hydrochlorofluorocarbon-152a (HCFC 152a), and compressed gases.10
Emission Sources
Aerosol Packaging--
Aerosol packaging process MC emissions may occur from the following
general sources: storage tanks, handling operations (e.g., mixing tank
loading), equipment leaks, wastewater, and accidental releases. Emissions
from these sources to the atmosphere would be from the following:
• Building openings, which would release MC emissions along with
other indoor air emissions;
• Process vents, which would release MC emissions directly from the
source to the atmosphere, without dilution by other indoor air
emissions; and
• Outdoor sources, which would include equipment used to store and
transfer MC, and on-site wastewater treatment facilities.4
126
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These MC emission sources from aerosol packaging processes are discussed in
the following paragraphs.
Methylene chloride storage tank emissions occur from breathing and
working losses. Breathing losses result from changes in barometric pressure
and temperature, and working losses result from volumetric changes in the tank
from filling or dispensing of stored solvent. Indoor storage tanks are
expected to have minimal or negligible breathing losses because of indoor
temperature controls that minimize diurnal temperature variation. Pressurized
tanks that have pressures greater than the atmospheric pressure are not
expected to have MC emissions.4 An example calculation of storage tank
emissions, using AP-42 methodology for storage of organic liquids, is
presented in Appendix A. Accurate estimation of storage emissions, as
discussed in Section 4, requires site-specific information.
Handling and transfer emissions result from filling and mixing tank
operations, aerosol can filling, and aerosol can washing. Filling and mixing
tank emissions are considered to be the most significant source of MC handling
emissions, and occur as the solvent is added (i.e., the filling) to the mixing
tank (as other ingredients are added), and during the mixing process itself.4
Estimation of handling and transfer emissions require the summation of
emissions from handling and transfer operations specific to a facility. The
reader is referred to AP-42, Section 4.0, Evaporation Loss Sources, for use as
a guideline in the estimation of these emissions.
Methylene chloride equipment leaks result from process equipment
components leaking in a liquid or gaseous state. These losses may occur
intermittently or continuously.4 An example calculation for estimating
emissions as a result of equipment leaks is presented in Appendix A.
Methylene chloride emissions that occur during on-site treatment and disposal
of wastewater, liquid waste, or solid waste are considered to be secondary
emissions.4 Appendix A contains a simplified example calculation for
estimating MC emissions from secondary wastewater treatment processes. For a
more detailed and accurate methodology for estimating MC emissions from
secondary wastewater treatment, the reader is referred to the EPA document
"Industrial Wastewater Volatile Organic Compound Emissions--Background
Information for BACT/LAER Determinations. EPA-450/3-90-004." As with MC
production, methodologies to estimate emissions require site-specific
parameters in order to represent emission potential accurately.
127
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Methylene chloride emission controls that may be incorporated in the
aerosol packaging process include storage tank refrigerated condensers,
process vent carbon adsorbers, and process vent refrigerated condensers. The
use of refrigerated condensers lowers the vapor pressure, and therefore, the
emission potential of the solvent. Additional control techniques with
associated control efficiencies for emissions of chlorinated solvents from
aerosol packagers is shown in Table 31.4 Methylene chloride evaporation
losses may also be controlled by the use of external or internal floating-roof
tanks in place of fixed-roof tanks. Control efficiencies for these tanks vary
according to the size of the tank and the type of seal employed.
Aerosol Dispensing Processes--
Emission of MC from aerosols result from the use of the product, and the
crushing, compacting, leakage, corrosion, and permeation of the aerosol
container that contains MC. Methylene chloride emissions from the consumption
of aerosol products result from the volatilization of suspended droplets or by
evaporation from sprayed surfaces.
Methylene chloride emission controls that may be employed include
minimization of MC content and integrity maintenance of the aerosol container.
Emission Estimates
Aerosol Packaging Process Emission Estimates--
Methylene chloride emission estimates from aerosol packaging processes,
based on Section 114 responses in 1987, were determined and documented in 1988
under a previous EPA project.12 Emissions were estimated for storage tanks,
handling operations, indoor and outdoor equipment leaks, secondary sources,
and accidental releases. The calculation procedures are documented in another
memo.12 Estimates of emissions from 10 of the 11 1987 Section 114 responses
were used to determine MC emissions for the remaining 184 facilities that used
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TABLE 31. CONTROL TECHNIQUES FOR EMISSIONS OF CHLORINATED SOLVENTS FROM AEROSOL PACKAGERS (1988)
Emission Reduction
Emission Source Control Technique Efficiency (%)
Storage tank Refrigerated condenser 95
Mixing Tanks (Handling) Carbon Adsorption3 95
Refrigerated condenser3 95
Equipment Leaks
Pump Seals (packaged and mechanical) Monthly LDAR 61
Flanges None Analyzed
Valves (liquid) Monthly LDAR 59
Valves (gas) Monthly LDAR 78
Sample Connections Closed-purge sampling 100
Open-Ended Lines Caps on open ends 100
Secondary Sources None analyzed 0
Source: Reference 4.
a Control option also includes covering the mixing tank and installing ductwork from the mixing tank
to the adsorber or condenser to recover chlorinated solvent emissions.
LDAR = Leak Detection and Repair
-------
MC in their aerosol products filled.12 Table 32 presents the emission
estimates from these 10 Section 114 responses.
The MC consumption reported in the 10 Section 114 responses was
8,400 Mg/yr, and reported emission estimates were 81.4 Mg/yr. An emission
factor for the entire aerosol packaging process, based on the uncontrolled
aggregate emissions/consumption for these 10 questionnaire respondents, is
0.01 Mg/Mg MC consumed (19.4 Ib/ton consumed),13
Aerosol Dispensing Process Emission Estimates--
There are no MC emission estimates available for the use of aerosol
products at this time. Trends away from MC use in aerosol products, however,
should reduce emissions proportionately to the reduction of use. Methylene
chloride content is ultimately considered to be released to the environment
via differing media (e.g. soil, air, and water). The only emission factor
found in the literature for aerosol products use was the worst-case assumption
that MC emissions are 1 kg/kg MC contained in product applied (2000 Ib/ton
MC contained in product applied).13
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TABLE 32. ESTIMATED METHYLENE CHLORIDE EMISSIONS FROM AEROSOL PACKAGERS IN 1987
Methylene Chloride Emissions (Mg/yr)
I-1
W
I-1
Company Name
New York Bronze Powder Co.
New York Bronze Powder Co.
Percy Harms corporation
Plaze, Inc.
Seymour of Sycamore
Sherwin-Williams Co.
Sherwin-Williams Co.
Sherwin Williams Co.
Speer Products
Zep Manufacturing
Total
Source: Reference 4.
Location
Elizabeth, NJ
Taylor, PA
Wheeling, IL
St. Louis, MO
Sycamore, IL
Anaheim, CA
Bedford Heights, OH
Elk Grove village, IL
Memphis, TN
Atlanta, GA
Total
18
24
0
2
5
4
9
0
13
1
81
.1
.9
.6
.4
.8
.5
.6
.8
.2
.5
.4
Storage
6.
2.
Oa
0.
0.
0.
2.
0.
1.
0.
14.
.6
.6
.5
.2
.3
.0
.2
.4
.2
.0
Handling
8
18
0
0
5
4
6
Oa
11
0
55
.3
.1
.4b
.6
.5°
.1
.1
.6
.8
.5
Equipment
Outdoor
NR
NR
NR
NR
0.1
NR
0.5
0.3
0.03
0.3
1.2
Leaks
Indoor
3
4
0
1
<0
0
1
0
0
0
10
.2
.2
.2
.3
.1
.1
.0
.3
.2
.2
.7
Secondary
NR
NR
NR
NR
NR
NR
NR
NR
NR
< .01
< .01
a A pressurized tank is used to store MC at this facility.
b Estimate includes 0.2 Mg/yr for aerosol can washing.
c Estimate includes 1.3 Mg/yr for aerosol can washing.
d No mixing operations are used at this facility because aerosol ingredients are added directly from storage to the product containers.
NR = Not reported.
-------
REFERENCES FOR AEROSOL PACKAGING AND DISPENSING
1. J.M. Reynolds, Cost Effective Replacements for Chlorinated Solvents and
Glycol Ethers, Spray Technology and Marketing, Industry Publications,
Inc., Fairfield, NJ, July 1991.
2. L.W. Patrick, Spray Technology and Marketing. Industry Publications,
Inc., Fairfield, NJ, December 1991.
3. Occupational Safety and Health Administration Proposal for New Methylene
Chloride Standard, 56 FR 57046-57047, 57068-57059, November 7, 1991.
4. "Emission Estimates and Controls from those Aerosol Packaging Facilities
Responding to Section 114 Questionnaires," Memorandum from J. Martinez,
R. Wassel, and G. Bockol, Radian Corporation, Research Triangle Park,
NC, to the Methylene Chloride Source Category Investigations File, U.S.
Environmental Protection Agency, Research Triangle Park, NC,
October 13, 1987.
5. "Chemical Profile--Methylene Chloride," Chemical Marketing Reporter,
241(9):42, March 2, 1992.
6. "Documentation of Telephone Communications Concerning the Packaging and
Localized Large-Scale Users of Aerosol Products," Memorandum from
G. Bockol, Radian Corporation, Research Triangle Park, NC, to the
Methylene Chloride Source Category Investigations File,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
February 6, 1987.
7. "Methylene Chloride Use in Aerosols as Compared with 1987 Uses,"
Telephone communication from Joanne O'Loughlin, Radian Corporation,
Research Triangle Park, NC, with Stephanie Kubik, Sprayon Products -
Division of the Sherwin-Williams Company, March 25, 1992.
8. "Chemical Profile--Methylene Chloride," Chemical Marketing Reporter,
February 20, 1989.
9. Volatile Organic Compound Emissions from Consumer and Commercial
Products, Aerosol Products and Packaging Systems, Report to Congress,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
December 1991.
10. Aerosol Products Workshop Summary, EPA Contract Number 68-02-3816,
U.S. Environmental Protection Agency, Research Triangle Park, NC, and
the Chemical Specialties Manufacturers Association, Washington, DC,
October 24, 1990.
11. Industrial Wastewater Volatile Organic Compound Emissions -- Background
Information for BACT/LAER Determinations, Chapter 4, EPA-450/3-90-004,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
March 1990.
12. "Documentation of Baseline and Controlled Emission Parameters for
Aerosol Packagers," Memorandum from E. Moretti, Radian Corporation,
Research Triangle Park, NC, to the Methylene Chloride Source Category
Investigations File, U.S. Environmental Protection Agency, Research
Triangle Park, NC, January 19, 1988.
132
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REFERENCES FOR AEROSOL PACKAGING AND DISPENSING (Continued)
13. Crosswalk/Air Toxic Emission Factor Data Base Management System (XATEF)
Version 1.2, Diskette, U.S. Environmental Protection Agency, Research
Triangle Park, NC, 1991.
133
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134
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MISCELLANEOUS
Approximately 5 percent of the total U.S. consumption of MC is for
miscellaneous uses such as pesticide manufacture, photographic film
processing, food processing, rubber cement and rubber accelerator manufacture,
dye carrying, solid waste treatment, storage and disposal (TSD), and site
remediation. Information gathered on pesticide manufacture and photographic
film processing, the largest two MC users in this miscellaneous group, are
discussed briefly in the following text. In addition, MC use in paints and
coatings is outlined.
Pesticide Manufacturing
Methylene chloride may be used in two areas of the pesticide industry:
(1) the manufacture of the pesticide; and (2) the formulation of the
pesticidal materials with the necessary additives and inert carriers.
Previous studies indicate that there are about 140 individual pesticide
manufacturing facilities and 200 to 300 formulation plants located throughout
the United States.1'2 However, only a fraction of these may use MC.1 One
source estimates that 60 manufacturers/formulators use 10 million pounds of MC
per year.3 The location of these facilities or the amount, if any, of MC used
by each were not verified in this study.
Methylene chloride has several applications in the pesticide
manufacturing industry, including extraction, phase separation, purification,
crystallization, and as a general transport solvent.1 In the formulation of
pesticide products, MC is sometimes used as a solvent to produce liquid
products from granular active ingredients.3 However, according to OSHA, there
is an indication that MC usage in pesticide processes will soon be phased out
because of health concerns. Products that have been substituted for MC
included petroleum distillates, aqueous formulas, mineral spirits, and
Agatane.3
Because of concern that some inert ingredients in pesticide products
might cause adverse effects in humans or the environment, EPA developed a
regulatory policy for inert ingredients.4 The EPA divided the approximately
1,200 inert ingredients contained in pesticide products into four toxicity
categories: Lists 1 and 2 contain inerts of toxicological or potentially
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toxicological concern, and Lists 3 and 4 contain inerts of unknown toxicity or
minimal concern. Methylene chloride is found on List 1. According to one
pesticide formulator, List 1 chemicals can be used in pesticides as long as
there is a warning on the product label, but to his knowledge, most of the
constituents (such as chlorinated solvents) are no longer used in these
products.5
Process Description--
The methods and exact technology for manufacturing pesticides varies
considerably depending on the type of pesticide, but MC is frequently used in
certain manufacturing steps. The pesticide industry employs the same unit
processes and operations used in the chemical processing industry.1 These
include chemical reactions, filtering, separation operations, condensation,
and drying. Production processes are usually carried out at ambient or
slightly above ambient temperatures. Elemental chlorine is the raw material
common to most pesticide production and is also frequently used to prepare
other raw materials used for pesticide production.
Emissions--
Air emissions from pesticide facilities include particulates, gases, and
vapors that may emanate from process equipment at each step of the
manufacturing process.1 Sources include process vents, storage, transfer,
handling, equipment leaks, and wastewater. An inspection of one pesticide
manufacturing facility revealed 26 potential sources (e.g., pellet mill,
grinding unit, Munson mixer, bagging unit) of air pollution and 13 emission
points (e.g., baghouse/cyclone, exhaust hoods, vents, and fans).6 The MC
emissions from three of these emission points can be found in Table 33.6
A comprehensive survey of typical control techniques and control levels
for pesticide manufacturing/formulating was not undertaken. However, control
techniques employed by several pesticide facilities using MC include
condensers, recycling systems, and incinerators.1 In general, applicable
control techniques would be similar to those discussed in Section 4 for
MC production.
136
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TABLE 33. EMISSIONS FROM THREE POINTS AT A PESTICIDE FACILITY, 1988
MC Emissions
Source kg/yr (Ib/yr)
Pellet Mill 334.7845 (738)
Marion Mixer 431.1803 (951)
Liquid Blending Area #1 12.4344 (27)
Source: Reference 6.
NOTE: Emission data are for one facility only and do not represent
average emissions for all such sources, or total emissions
for all sources.
137
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Photographic Film Manufacture
Methylene chloride is a key component in the manufacture of cellulose
triacetate-based films. It is used with heat to dissolve cellulose triacetate
pellets in order to produce a fine, transparent layer which is rolled onto
photographic paper. This layer must be transparent, durable, and flexible.
Other materials used in the manufacturing process are plasticizers and small
amounts of other solvents.9 Virtually all still camera, graphic arts, and
photographic films in use in the United States are cellulose triacetate-based.
Substitutes for MC in this process have not been identified.7
Photographic film is currently produced at two sites. The largest
facility is owned and operated by Eastman Kodak, with a facility located in
Rochester, New York. This plant consumes approximately 4 Mg (9 million
pounds) of MC annually.8 Anitec Image Technology Corporation in Binghampton,
New York uses approximately 0.9 Mg (1.9 million pounds).9
Process Description--
Several steps are required in the development of cellulose triacetate
film. These steps are represented in Figure 18. Methylene chloride,
plasticizers, cosolvents, and solid cellulose triacetate pellets are heated to
produce a thin slurry called "crude dope." The dope is 60-65 percent MC by
weight.9 Vapors from this melting process are recovered by use of
distillation equipment. The crude dope is then transported through the
filtration process by use of a continuous screen, continuous wash, and
multiscreen filters. This process is completed in a closed system; however,
the continuous wash and multiscreen filters are changed four to five times per
day.
The filtered dope is no longer considered crude at this point. It is
fed into a receiving hopper that extrudes dope onto a large, polished
cylindrical wheel, called a rollcaster. The dope is trimmed from the wheel,
leaving a thin sheet or "web" that is dried at 121-138°C in an enclosed
chamber. The MC is nearly completely evaporated in this process. The roll
casting process is operated in a semi-enclosed manner, with some of the
evaporating MC removed, and the remainder exhausted to the atmosphere.9
138
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Methylene
Chloride
Storage Tank
Receiving
Hopper
Building Vent Emissions
Continuous Wash
Press Filter
Roll Coating
(on Photographic Paper)
Conveyor
Distribution
Figure 18. Photographic film process with MC emission sources.
-------
Emissions--
Emissions from the manufacture of cellulose triacetate-based film can
result from three basic stages of production: dope preparation, roll coating,
and distillation or recycling. Numerous emission sources have been
identified, but data have only been released for the most significant sources.
Dope production is the process of dissolving cellulose triacetate
pellets. This is generally initiated by use of continuous mixers; however,
batch mixers may be occasionally used. Emissions can be significant when
these pellets are introduced to the mixing chamber during batch mixing.
Current emission estimates for this activity are not available because the
frequency of batch mixing has decreased markedly in recent years. Two other
significant emission points in the dope production phase occur when filters
for the continuous wash, transfer, and multipress filtration units are
changed.9'13 This process occurs approximately twice per day for each unit.
The filters are removed from a cylindrical housing and allowed to evaporate.
Emissions from this process have been estimated to be higher than all other
dope production sources.
All other sources of MC emissions from dope production are associated
with storage tanks and general building ventilation. The largest of these
points are from "floor sweeps." These are ducted vents located near the
filter housings that exhaust MC that accumulates near the floor.
Emissions from the roll coating machine represent over 90 percent of the
emissions at a typical facility. During solvent evaporation of the film base
web, local exhaust ventilation transports vapors to distillation and condenser
recovery systems. This system recovers approximately 95 percent of the
MC vapors in the process. The remaining 5 percent are released into the
building, which has a ventilation design to rapidly move vapors from the floor
and out of the building through vents or stacks. Large volumes of MC and the
high temperatures at which the system operates account for the high level of
emissions relative to other process functions. The building ventilation
system, which serves primarily as a method to reduce workers' exposures, may
also contribute to the building emissions.9
140
-------
The other major process function in the manufacture of cellulose
triacetate film is the distillation of recovered vapors. The major point of
emissions from this source are likely to be storage tanks associated with the
process.
Control technologies at the Kodak Rochester facility have included
carbon adsorbers, scrubbers, condensers and vapor return. The exact locations
of many of these controls have not been released. However, several control
methods are used to recover MC. Carbon adsorbers have been applied at the
roll coating machines exhaust air and building openings. Scrubbers have been
applied in the solvent recovery systems. Reliable estimates of control
efficiencies for these systems are not available. Other controls for fugitive
emissions have included the selection of new valves with tighter seals and an
increase in inspection and maintenance of existing potential process leaks.
The pending OSHA regulations may significantly affect the type of controls
that may be implemented.
Paints and Coatings
The paint and coatings industry encompasses a wide variety of products
with many different end uses. A paint or coating is defined as a "liquid,
liquefiable, or mastic composition that is converted to a solid, protective,
decorative or functional adherent film by the application of a thin layer."10
Paints and coatings are produced by an estimated 390 facilities that
consume 12,700 Mg of MC annually.11 Paint and surface coatings are formulated
by mixing three elements: synthetic polymer resins, which act as a binding
agent, a dispersion medium (water or a volatile solvent), and pigments.
Methylene chloride may be used in some products as a cosolvent in the
dispersion medium to promote faster drying and dissolve binders during
application. The main ingredients used in solvent-based paints are mineral
spirits or petroleum naphtha products. Because MC reacts with dried paints on
previously painted surfaces, its composition in paints is relatively low --
one or two percent by weight.11
For paints and coating products, recent emphasis on production of low-
VOC products may increase the demand for additional MC use as a cosolvent
because MC may be exempted from regulation as a VOC under state regulations
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implementing the national ambient air quality standard for ozone.12 The
impact of these regulations, however, is highly speculative at this time.
Methylene chloride emissions data for paints and coatings formulation
and use was not found.
142
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REFERENCES FOR MISCELLANEOUS SECTION
1. Survey of Methylene Chloride Emission Sources, EPA-450/3-85-015,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
June 1985.
2. T. Ferguson, Pollution Control Technology for Pesticide Formulators and
Packagers, EPA-660/2-74-094. U.S. Environmental Protection Agency,
Research Triangle Park, NC, January 1975.
3. Occupational Safety and Health Administration Proposal for New Methylene
Chloride Standard, 56 FR 57053, 57069, November 7, 1991.
4. Inert Ingredients in Pesticide Products; Policy Statement, 52 FR 13305,
April 22, 1987.
5. Written communication from Jim Case, S.C. Johnson & Son, Inc., Racine,
WI, to Candace Blackley, Radian Corporation, Research Triangle Park, NC,
September 10, 1991.
6. High Risk Point Source Study for the Formulation of Pesticides and
Agricultural Chemicals at Southern Mill Creek Products, Inc. (SMCP),
Tampa, Florida, Air Toxics Section of the Environmental Protection
Commission of Hillsborough County, pp. 1-9, Appendix E, May 1990.
7. S.A. Walata and R.M. Rehm, Source Characterization and Control
Technology Assessment of Methylene Chloride Emissions from Eastman Kodak
Company, Rochester, New York, EPA-600/2-89-043. U.S. Environmental
Protection Agency, Research Triangle Park, NC, 1989.
8. White Paper -- Methylene Chloride. Halogenated Solvents Industry
Alliance, Washington, DC, February 1989.
9. Occupational Safety and Health Administration Proposal for New Methylene
Chloride Standard, 56 FR 57066, November 7, 1991.
10. "Paint--Tests for Formulated Products and Applied Coatings," 1990 Annual
Book of ASTM Standards, Volume 06.01, R. Storer, et al. eds., American
Society for Testing and Materials, Philadelphia, PA, 1990.
11. Occupational Safety and Health Administration Proposal for New Methylene
Chloride Standard, 56 FR 57102, November 7, 1991.
12. "Summary of Information Obtained Through Telephone Contact with
Formulators, Distributors, and Users of Methylene Chloride-Based Paint
Strippers," Memorandum from I. McKenzie, Radian Corporation, Research
Triangle Park, NC, to the Paint Stripping Facilities Project File,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
January 22, 1987.
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SECTION 6
SOURCE TEST PROCEDURES
Methylene chloride emissions can be measured by a combination of
the following methods:1 (1) EPA Method 0030; (2) EPA Method 5040;
(3) EPA Method 5041; (4) EPA Method 18; (5) Compendium Method TO-1;
(6) Compendium Method TO-2; (7) Compendium Method TO-14; and (8) NIOSH
Method 1005. Each of these methods is discussed in the following
paragraphs.
EPA METHOD 0030
EPA Method 0030, which was published in EPA Report No. SW-8462 in
November, 1986, is a sampling method used to determine the destruction
and removal efficiency (DRE) of volatile principal organic hazardous
constituents (POHCs) from stack gas effluents from stationary sources.
EPA Method 0030 is used for sampling MC emissions from stack gas
effluents.1 This methodology is applicable for sampling volatile
constituents with boiling points between 35°C and 100°C; the boiling
point of MC is within this range.
In Method 0030, a sample of effluent gas is withdrawn from an
emission source using a glass-lined probe and a volatile organic
sampling train (VOST). The gas stream is cooled through a water-
cooled condenser and volatile POHCs are collected on a pair of sorbent
resin traps, the first containing Tenax® and the second containing
Tenax® and petroleum-based charcoal. Liquid condensate is collected
in an impinger placed between the two resin traps. A schematic
diagram of the VOST system is shown in Figure 19.
The sensitivity of this method depends on the level of
interferences in the sample and the presence of detectable levels of
volatile POHCs (in this case, MC) in the blanks. Interferences can
arise from contamination of sorbent traps prior to or after use in
sample collection.3 Exposure of the sorbent materials to solvent
vapors prior to assembly can be one source of interferences. Because
MC is a common field recovery solvent, laboratory solvent, and
laboratory air contaminant, contamination of the sorbent traps from
these sources can also be a problem. Exposure to significant
concentrations of volatile POHCs such as MC in the ambient air at
chemical plants and other sources previously discussed is another
145
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Glass Wool
Paitlcidata
filter
Stack
(or test system)
Exhaust
Silica Gel
Source: Reference 2 Condensata Trap Imping**
Figure 19. Schematic of volatile organic sampling train (VOST).
i
-------
potential interference. A sufficiently high background level in the
source can make it impossible to determine trace quantities in the
samples.
EPA METHODS 5040 AND 5041
EPA Methods 5040 and 5041 are both used to analyze POHCs
collected from stack gas effluents of stationary sources. Method 5040
was published in the November 1986 Report No. SW-846.2 Methods 5040
and 5041 are the primary analytical methods for determining the
concentration of MC in stack emissions sampled using the VOST Method,
EPA Method 0030.1 The combination of Methods 0030/5040 or 5041 is
intended for trace levels of organic compounds in emissions
(i.e., ppb, low ppm). If the concentration in the source is hundreds
of ppm or percentage levels, these methods are not appropriate.
Because the majority of gas streams sampled using VOST will contain a
high concentration of water, the analytical method is based on the
quantitative thermal desorption of volatile POHCs from the Tenax® and
Tenax®/charcoal traps. Purge-and-trap gas chromatography/mass
spectrometry (GC/MS) is used to perform the analysis. The major
difference between Methods 5040 and 5041 is the analytical column
required. In Method 5040, a packed glass column is used; a Megabore®
capillary column is used in Method 5041.
A schematic diagram of the analytical system is shown in
Figure 20. The sorbent cartridges are spiked with internal standards
and surrogates, thermally desorbed, and the VOCs are trapped on an
analytical adsorbent trap directed into the GC/MS. The volatile POHCs
are separated by temperature-programmed GC and detected by low-
resolution MS.
The concentrations of volatile POHCs are calculated using the
internal standard technique. Sample trains obtained from the VOST
should be analyzed within two to six weeks of sample collection. The
desired target detection limit of these methods is 0.1 nanogram per
liter (ng/C) (20 ng on a single pair of traps).
As with VOST sampling, solvent contamination can occur with
analysis. Therefore, appropriate use of laboratory and field blanks
is crucial for obtaining accurate quantitative values. Other concerns
that may need to be addressed when using Methods 5040 and 5041 include
147
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CD
Thermal
Dmorptlon
Chamber
I
Flow to
GO/MS
Flow During
Desorptlon
Flow During
J
HeorN2
Adsorption
©'©©©
xx
Analytical Trap
with Heating Coil
(0.3 cm diameter
25 cm long)
Vent
3%CV 1 (1cm)
TENA>P(7.7cm)
(V) Silica Gel (7.7 cm)
(7) Charcoal (7.7 cm)
Source: Referenced
Figure 20. Schematic diagram of trap desorption/analysis system.
-------
saturation of the sampling cartridges with the analyte (MC) or other
compounds found in the stack gas emissions, and background
interferences during analysis.
Interferences occur when something impairs the analyst's ability
to make an accurate determination. In the case of a chromatographic
method, this impairment is usually due to the presence of coeluting
peaks that may arise from contamination of the sampling medium
(sorbents). However, major sources of interference are constituents
of the background during sampling. Many sources have a moderate to
high background of hydrocarbons, some of which may coelute with MC and
which may have common mass spectral ions. Other constituents of the
source background may also provide chromatographic and mass spectral
interference that will impair the ability of the analyst to perform an
accurate determination.4
EPA METHOD 18
EPA Method 18 was announced in the Federal Register on
October 18, 1983, and is published in Appendix A of 40 CFR Part 60.5
It applies to the sampling and analysis of approximately 90 percent of
the total gaseous organics emitted from an industrial source.1
Method 18 is an alternative sampling and analytical method for VOCs
(including MC). It can be used for single analytes or for a small
number of multiple analytes. Method 0030, combined with Methods 5040
or 5041, has a broader application to a wider range of analytes and
may, therefore, be preferred if there is a need to analyze for many
organics. Method 18 has been used extensively for testing emissions
from the chemical industry and other source categories emitting VOC.
In Method 18, a sample of the exhaust gas to be analyzed is drawn
into a Tedlar® or aluminized Mylar® bag, as shown in Figure 21.5 The
bag is placed inside a rigid, leakproof container and evacuated. The
bag is then connected by a Teflon® sampling line to a sampling probe
(stainless steel, Pyrex®
glass, or Teflon®) at the center of the stack. The sample is drawn
into the bag by pumping air out of the rigid container.
The sample is then analyzed by GC coupled with flame ionization
detection (FID). Based on field and laboratory studies, the
recommended time limit for analysis is within 30 days of sample
149
-------
Vent
Ul
o
Fitter
(glass wool)
%,
Revere*
'?*.
Slack WaH
Male Quick
Connectors
Flowmeter
Probe
Teflon* Sample Line
1 3
Bad Check
Pilot Manometer
Vacuum Una
Neede Valve
Charcoal
Tube
3
Pump
No Check
Rigid Laakproof Container
Source: References
Figure 21. Integrated bag sampling train.
-------
collection.3 The GC operator should select the column and
GC conditions that provide good resolution and minimum analysis time
for MC. Zero grade helium or nitrogen should be used as the carrier
gas at a flow rate that optimizes the chromatographic resolution.
The peak areas corresponding to the retention times of MC are
measured and compared to peak areas for a set of standard gas mixtures
to determine the MC concentrations. The detection limit of this
method ranges from about 1 part per million (ppm) to an upper limit
governed by the FID saturation or column overloading. However, the
upper limit can be extended by diluting the stack gases with the inert
gas or by using smaller gas sampling loops.
When access to the sampling location is difficult, an alternative
sampling method described in Section 7.4 of EPA Method 18 may be
preferred.3
COMPENDIUM METHODS TO-1, TO-2, AND TO-14
Compendium Methods TO-1, TO-2, and TO-14 are sampling and
analytical methods used to determine VOCs such as MC in ambient air,
and can be found in the "Compendium of Methods for the Determination
of Toxic Organic Compounds in Ambient Air."6 These methods are not
appropriate for source monitoring.1
Method TO-1
Method TO-1 is used to collect and determine volatile, non-polar
organics that can be captured on Tenax® and determined by thermal
desorption techniques. In this method, air is drawn through a
cartridge containing 1-2 g of Tenax®. The cartridge is analyzed in
the laboratory for MC and purged with an inert gas into a GC/MS
system. Only capillary GC techniques should be used. The GC
temperature is increased through a temperature program and the
compounds are eluted from the column on the basis of boiling points.
The MS identifies and quantifies the compounds by mass fragmentation
patterns. Compound identification is normally accomplished using a
library search routine on the basis of GC retention time and mass
spectral characteristics.
151
-------
Method TO-2
In Method TO-2, air is drawn through a cartridge containing 0.4 g
of a carbon molecular sieve (CMS) adsorbent. The cartridge is
analyzed in the laboratory by flushing with dry air to remove adsorbed
moisture and purging the sample with helium while heating the
cartridge to 350-400°C. The desorbed organics (such as MC) are
collected in a cryogenic trap and flash-evaporated into a GC/MS
system. Only capillary GC techniques should be used. The
GC temperature is increased through a temperature program and the
compounds are eluted from the column on the basis of boiling points.
The MS identifies and quantifies the compounds by mass fragmentation
patterns. Compound identification of MC is normally accomplished
using a library search routine on the basis of GC retention time and
mass spectral characteristics.
Method TO-14
Method TO-14 is based on the collection of whole air samples in
SUMMA® passivated stainless steel canisters for analysis of VOCs (MC)
in ambient air. A sample of ambient air is drawn through a sampling
train of components that regulate the rate and duration of sampling
into a pre-evacuated SUMMA® passivated canister. The canister is
attached to the analytical system. Water vapor may be reduced in the
gas stream by a Nafion® dryer and VOCs are concentrated by collection
into a cryogenically-cooled trap. The cryogen is removed and the
temperature of the sample raised to volatilize the sample into a high-
resolution GC. The GC temperature is increased through a temperature
program and the compounds are eluted from the column on the basis of
boiling points into a detector.
The choice of detector depends on the specificity and sensitivity
required by the analysis. Gas chromatography ultimately relies on
retention time for identification of compounds. In many cases, this
use of retention time is enhanced by the information from a selective
gas chromatographic detector. However, it cannot be determined from
GC alone whether coelution of compounds is occurring, or whether a
particular peak represents a particular compound. When mass
spectrometry is used as the detector, a mass spectrum can provide
compound-specific information and can show whether other compounds are
present at a given retention time.4
152
-------
In Method TO-14, a capillary column with methyl silicone coating,
or equivalent is specified for detecting MC.6 A wider Megabore® column
can be used as long as the system meets user needs. Compounds have
been successfully measured at the parts per billion by volume (ppbv)
level using this method.
NIOSH METHOD 1005
The NIOSH methods are used to measure ambient air in workplace
environments. NIOSH Method 1005, which was published in the 1985
"NIOSH Manual of Analytical Methods", is used to measure MC in the
workplace.7
In NIOSH Method 1005, air samples are collected with solid
sorbent tubes containing coconut shell charcoal. A personal sampling
pump is used to collect 1.5 - 2.5-0 air samples at a flow rate of 0.01
to 0.2 0/min. Samples are desorbed with carbon disulfide and analyzed
by GC equipped with an FID. The column specified in NIOSH Method 1005
is a 3.0 m x 3 mm stainless steel, 10% SP-1000 on 80/100 mesh
Chromosorb® W-HP, or equivalent.7 The amount of MC in a sample is
obtained from the calibration curve in units of milligrams per sample.
The working range of NIOSH Method 1005 is 100 to 3000 ppm for a 1-0
air sample. The method is applicable to ceiling determinations.
153
-------
REFERENCES FOR SECTION 6
1. Screening Methods for the Development of Air Toxics Emission
Factors, EPA-450/4-91-021, U.S. Environmental Protection Agency,
Research Triangle Park, NC, September 1991.
2. Test Methods for Evaluating Solid Waste, 3rd Ed., Vol. IB:
Laboratory Manual, Physical/Chemical Methods, EPA Report No.
SW-846, U.S. Environmental Protection Agency, Washington, DC,
November 1986.
3 . Locating and Estimating Air Emissions from Sources of Styrene,
Interim Report, EPA-450/4-91-029, U.S. Environmental Protection
Agency, Research Triangle Park, NC, September 1991.
4. Telephone communication between Candace Blackley and Joan Bursey,
Radian Corporation, Research Triangle Park, NC, March 26, 1991.
5. Code of Federal Regulations (Title 40, Part 60, Appendix A):
"Method 18: Measurement of Gaseous Organic Compound Emissions by
Gas Chromatography," 40 CFR 60, Appendix A.
6. Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air, U.S. Environmental Protection Agency,
Research Triangle Park, NC, May 1988.
7. NIOSH Manual of Analytical Methods, 3rd Ed., Volume 2,
U.S. Department of Health, Education, and Welfare, National
Institute for Occupational Safety and Health, Cincinnati, Ohio,
1987.
154
-------
APPENDIX A
EXAMPLE PROCEDURES TO ESTIMATE METHYLENE CHLORIDE EMISSIONS
The purpose of this appendix is to present general example equations or
calculation procedures and assumptions that may be used to estimate methylene
chloride (MC) air emissions from differing sources. This appendix describes
estimation procedures for three types of emission sources: (1) storage;
(2) equipment leaks; and (3) secondary sources (wastewater).
The following sections describe example estimation procedures for
emission sources.
A-l
-------
SECTION 1 - STORAGE EXAMPLE
The following storage loss equations are presented for estimating fixed-
roof breathing loss and fixed-roof working losses for a vertical tank storing
methylene chloride. The following example equations are from the EPA
Publication No. AP-42 emission factors for storage of organic liquids,
Supplement E.1 The purpose of their presentation is to alert the reader to
the site-specific and chemical property considerations that are required for
the estimation of MC emissions from storage. The equations presented are
based on the following general points:
• Equations are for estimating standing storage and working losses
for a vertical, fixed-roof storage tank.1
• Storage tank emissions from loading and unloading MC are accounted
for in the working loss equation.
Example Equations
For a vertical, fixed-roof storage tank the following equations apply:1
where: Ls = 365 WVVVKEKS
Lw = 0.0010 MVPVAQKNKP
LT = total loss, Ib/yr
Ls = standing storage loss, Ib/yr
Lw = working loss, Ib/yr
Vv = tank vapor space volume, ft3
v =
4 D^ Hvo
Wv = vapor density, lb/ft3
M,,P VA
KE = vapor space expansion factor, dimensionless
ATV APV - APB
Ks = vented vapor space saturation factor, dimensionless
A-2
-------
0.053PVAHVO
diameter, ft
vapor space outage, ft
Mv = molecular weight of vapor, Ib/lb-mole
PVA = vapor pressure at the daily average liquid surface
temperature, psia
TLA = daily average liquid surface temperature, °R
ATV = daily vapor temperature range, °R
APV = daily vapor pressure range, psia
APB = breather vent pressure setting range, psi
PA = atmospheric pressure, psia
Q = annual net throughput, Ib/yr
KN = working loss turnover factor, dimensionless
Kp = working loss product factor, dimensionless
Applicability Considerations:
Equations and tables that further define these equation variables
are presented in Supplement E of AP-42, "Storage of Organic
Liquids."
Emissions from horizontal tanks can be calculated by making
adjustments to parameters in the fixed-roof equations. There are
step-wise examples regarding how to proceed with adjustments in
Supplement E of AP-42, "Storage of Organic Liquids."
Supplement E also supplies the vapor pressure equation constants,
molecular weight, boiling point at 1 atmosphere, liquid density at
60°F, and vapor pressure at varying temperatures for a variety of
compounds (including MC).
A-3
-------
SECTION 2 - EQUIPMENT LEAKS EXAMPLE
The following equipment leaks example is presented for estimating
equipment leaks emissions based on VOC emission factors. This example
presents the simplest of five methods delineated in the "Protocols" document,
and should only be employed when other data are not available.2 The purpose
of its presentation is to alert the reader to the site-specific and chemical
property considerations that are required for the estimation of MC emissions
from equipment leaks. The estimation methodology is based on the following
general points:
• Annual emission rates from equipment leaks in this example are
based on the VOC emission factors (kg of VOC/hr) presented in
Table A-l.2
• In applying the emission factors to equipment leaks, MC can be
considered as a light liquid VOC because its vapor pressure is
greater than 0.3 kPa. It can be assumed that MC is emitted like
other VOC compounds.
• The annual MC emission rate from each equipment component type is
the product of the appropriate emission factor, the percent MC
handled by the equipment component, the maximum number of hours
the equipment handles MC-laden material, and the number of
equipment components that come in contact with the MC. The
emission rates for each type of equipment component (i.e., pump
seals, compressor seals, flanges, etc.) are summed to obtain a
total equipment leak emission rate for each facility.
Sample Calculation
Example Site-Specific Information
• Three mechanical pump seals between mixing tank and filling lines.
All are within a building.
3 lines - 3 pump seals
• Hours of handling
3 lines - 8 hr/day, 5 day/wk
• Amount of MC consumed = 496,944 Ib/yr. Includes consumption for
products and line flush.
• Amount of MC-based products packaged = 2,828,797 Ib/yr
A-4
-------
TABLE A-l. AVERAGE EMISSION FACTORS FOR PROCESS EQUIPMENT COMPONENTS
USED TO ESTIMATE VOC EMISSIONS FROM EQUIPMENT LEAKS
Equipment Component Emission Factora-b
(Emission Source) (kg VOC/hr-component)
Pumps - Liquid13 0.494
Compressors 0.228
Flanges 0.00083
Valves - Gas 0.0056
- Liquid13 0.0071
- Heavy Liquid 0.00023
Sampling Connections 0.0150
Open-Ended Lines 0.0017
a Emission factors were developed for VOC emitted from equipment components
used in the synthetic chemical manufacturing industry (SOCMI).
13 Liquid refers to light liquid and is defined as a petroleum liquid with a
vapor pressure greater than the vapor pressure of kerosene.
Source: Reference 2.
A-5
-------
Calculations
1. Hours of Handling = 8 hr/day • 5 day/wk • 52 wk/yr = 2,080 hr/yr
--assumes 52 wk/yr
2 . Percent MC handled by the equipment components
- 496,944 IbMC/yr - . = weight-percent
2,828,797 Ib MC-based product/yr
- assumes the amount of MC used for cleanup and line flush
is handled by the same component
- assumes concentration of MC is similar for all lines
3. Number of and emission factors for equipment components.
Number and type of equipment component = three mechanical pump seals.
Emission factor for pump seals = 0.494 kg MC/hr
A Annual Mr Fmi
-------
SECTION 3 - SECONDARY WASTE STREAM EXAMPLE
The following secondary waste stream wastewater example calculation is
presented as an example method for the estimation of MC emissions from
wastewater streams. For a more detailed and accurate estimation methodology
for MC emissions from wastewater streams, the reader is referred to the
"Industrial Wastewater Volatile Organic Compound Emissions -- Background
Information for Proposed Standards" document.3 The purpose of this
presentation is to alert the reader to some of the site-specific
considerations required for the estimation of MC emissions from wastewater
streams.
Example Method
• Secondary waste streams include wastewater streams, and organic-
liquid or solid wastes.
• Emissions from wastewater streams can be calculated from the MC
concentration, and the daily influent wastewater flowrate. In
order to develop maximum emission estimates, it could be assumed
that all of the MC in the wastewater is released to the
atmosphere. In this example, it is assumed wastewater is
generated 260 days per year.
Influent Wastewater Influent
Flowrate to Treatment • Concentration • [3.79 {/gal]
MC Emission Rate = or Storage [gal/day] [//g MC/f]
[Mg MC/yr] 10i2 ^g _ yr
1 Mg 260 day
• Emissions from organic-liquid or solid wastes can be calculated
from the daily volume of waste generated and the weight percent
of MC.
Emission Rate
[Mg MC/Yr] = Daily Volume . Density MC . 260 days . MC Composition
from Liquid or [gal/day] [Mg/gal] yr (wt-percent)
Solid Wastes
A-7
-------
REFERENCES
1. Compilation of Air Pollutant Emission Factors, Volume I: Stationary
Point and Area Sources, Fourth Edition, AP-42, Supplement E,
U.S. Environmental Protection Agency, Research Triangle Park, NC.
2. Protocols for Generating Unit-Specific Emission Estimates for Equipment
Leaks of VOC and VHAP, EPA-450/3-88-010, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1988.
3. Industrial Wastewater Volatile Organic Compound Emissions -- Background
Information for BACT/LAER Determinations, EPA-450/3-90-004, March 1990,
Chapter 4 .
A-!
-------
APPENDIX B
NATIONAL LIST OF PAINT STRIPPER FORMULATORS (JULY 1981]
B-l
-------
NATIONAL LIST OF PAINT STRIPPER FORMULATORS (JULY 1987]
Company Name
Location
Alvin Products, Inc.
Amchem Products
American Niagara Corp.
Ashland Chemical Co.
A-Z Midwest Factory Supply
Beaver Alkali Products
Beck Chemicals, Inc.
Behlen, H. & Bros., Inc.
Benco
Benco
Besway Chemical Systems, Inc.
Cedtex Chemical
Certified Coating Pdts., Inc.
Chemclean Corporation
Chemical Products Co., Inc.
Chemical Systems Research
Consolidated Chemical
Dap, Inc.
Day, James B., & Co.
Delta Foremost Chemical Corp.
Diversey Wyandotte Corp.
Dober Chemical Corp.
Dynaloy, Inc.
Dytex Chemical Co., Inc.
Ecco Chemicals, Inc.
Eldorado Chemicals
Ensign Products
Enterprise Co.
Excelda Mfg. Co.
Excelsior Varnish
EZE Products
Worcester, MA
Ambler, PA
Atlanta, GA
Columbus, OH
Addison, IL
Rochester, PA
Cleveland, OH
Amsterdam, NY
Fontana, CA
Crossville, TN
Madison, TN
Southfield, MI
Los Angeles, CA
College Point, NY
Aberdeen, MD
West Bloomfield, MI
St. Louis, MO
Tipp City, OH
Carpentersville, IL
Memphis, TN
Wyandotte, MI
Midlothian, IL
Hanover, NJ
Central Falls, RI
Dallas, TX
San Antonio, TX
Cleveland, OH
Wheeling, IL
Ferndale, MI
Cleveland, OH
Greenville, SC
B-2
-------
NATIONAL LIST OF PAINT STRIPPER FORMULATORS (JULY 1987]
(Continued)
Company Name
Location
Formby's Inc.
FPNS
Fuller-O'Brien Paints
Gage Products
Goodrich Products
Grow Group, Inc.
Grow Group, 2 (Nat'l Aerosol Pdts;
Harley Chemicals
Hexcel Chemicals
Higley Chemicals
Hillyard Chemicals
International Chemicals
International Paints
International Paints
Isochem Products
J & S Chemicals
Jasco Chemicals
KCI Chemicals
Kerns United
Key Chemicals
Klean Strip
Kwick Kleen Industries
London Chemicals
Lowe Brothers Co.
Madison Bionics
Magnuson Products
Man-Gill Co.
Mantrose-Hauser Company
McGean Rohco Inc.
Midland Lab
Mitchell-Bradford Chemicals
Olive Branch, MS
Henderson, KY
South San Francisco, CA
Ferndale, MI
Highlands, TX
Detroit, MI
Los Angeles, CA
Camden, NJ
Lodi, NJ
Dubuque, IA
St. Joseph, MO
Philadelphia, PA
Union, NJ
Houston, TX
Lincoln, RI
Macedonia, OH
Mountain View, CA
La Porte, IN
Calumet City, IL
Philadelphia, PA
Memphis, TN
Vincennes, IN
Bensenville, IL
Cleveland, OH
Oak Brook, IL
Clifton, NJ
Cleveland, OH
Attleboro, MA
Los Angeles, CA
Des Moines, IA
Milford, CT
B-3
-------
NATIONAL LIST OF PAINT STRIPPER FORMULATORS (JULY 1987]
(Continued)
Company Name
Location
National Solvent Corp.
NCH Corp.
Nuvite Chemicals
Oakite Products
Oakite Products
Oakite Products
Oakite Products
Oxford Chemicals
Par-Chem Products
PENS
Penetone Corporation
Pennwalt Corporation
Pennwalt Corporation
Petrocon Marine & Ind.
Pioneer Chemicals
Prillaman Company
Product-Sol Inc.
Proko Industries
PyRock Chemicals
Rap Products
Red Devil Paints
Reliable Paste and Chemicals
Reliable Remover and Lacquer
Savogran Company
Savogran Company
Savogran Company
Sermac Industries
Sheldahl
Sherwin-Williams
Sherwin-Williams
Staples, H.F.
Medina, OH
Irving, TX
Brooklyn, NY
Metuchen, NJ
City of Industry, CA
Romulus, MI
Houston, TX
Atlanta, GA
Houston, TX
Henderson, KY
Tenafly, NJ
Carson, CA
Marion, OH
Brooklyn, NY
West Point, OH
Martinsville, VA
Birmingham, MI
Dallas, TX
Long Island City, NY
Bay City, MI
Mount Vernon, NY
Chicago, IL
Irvington, NJ
Norwood, MA
Addison, IL
Los Angeles, CA
Altoona, PA
Northfield, MN
Richmond, KY
Chicago, IL
Merrimack, NH
B-4
-------
NATIONAL LIST OF PAINT STRIPPER FORMULATORS (JULY 1987)
(Concluded)
Company Name Location
Star Bronze Alliance, OH
Sterling-Clark-Lurton Maiden, MA
Strip-Tech Hendersonville, TN
Stripping Products (BIX) Old Hickory, TN
Stuart Radiator Merced, CA
Sunshine Chemicals West Hartford, CN
Texas Refinery Fort Worth, TX
Texo Corp Cincinnati, OH
Tower Chemicals Palmer, PA
Tropical Industrial Coatings Brunswick, OH
United Gilsonite Scranton, PA
Urban Chemicals Deerfield, IL
Watson-Standard Harwick, PA
William M. Barr & Co. Memphis, TN
Wilson-Imperial Newark, NJ
Zep Manufacturing Atlanta, GA
Source: Memorandum from E. Moretti, Radian Corporation, to the
U.S. Environmental Protection Agency. Emission
Estimates and Controls for Emissions from Paint
Stripper Formulation Facilities (DRAFT). September 11,
1987.
B-5
-------
APPENDIX C
NATIONAL LIST OF AEROSOL PACKAGERS
C-l
-------
NATIONAL LIST OF AEROSOL PACKAGERS (JULY 1987)
O
1
2
1
4
i
6
7
•
9
10
11
12
13
1*
14
16
17
11
19
20
21
22
23
2*
25
26
27
20
29
30
31
32
33
34
35
16
1>
IB
If
COMPANY
ACCRA PAC GROUP
ADTECH DESIGN CO.
ADVANCE AEROSOL t CHEMICAL CO.
AEROSOL RESEARCH LAI, INC.
AEROSOL SERVICES CO.. INC.
AEROSOL SYSTEMS
AEROSOL WEST
AEROTECH INDUSTRIES
AERO-KING, INC.
AERVOE PACIFIC CO.
AIROSOL CO.. INC.
ALTAUOOO INC.*
AMERICAN AEROSOLS
AMERICAN NIAGARA CORP.
AMREP, INC.
AMVIAY CORP.
APOLLO INDUSTRIES, INC. *
ATI, INC-1
ATI, INC-2 (ARMSTRONG LABORATORIES DIV.)
BARR CO.
BARRETT CHEMICAL CO.
BEECHAM HOME IMPROVEMENT
BISSELL-1 (PENN CHAMP, INC)
BISSELL-2 (PENN CHAMP, IMC)
BORDEN (KRYLOM DEPARTMENT)
10XAL METALS, INC.
BOYLE-MIDWAY (AMERICAN HOME PRODUCTS)
BRISTOL-MEYERS-1 (CLAIROL)
BRISTOL-HEYERS-2 (LENK CO.)
BROUGHTON FOODS CO.
BIB AEROSOL PACKAGING CO., INC.
CAM1E CAMPBELL. INC
CARE LABORATORIES. INC
CARSON CHEMICALS. INC
CARTER WALLACE. INC
CASE HASON FILLING. INC
OIAMMON I.ABS (I'YKOII. CM )
CIIASt. I'HOIHH |s CD
•'.Wrt TK II |Hi:
CITY
ELKHARDT
II/IBCHAM
IHJHalMin
GENOA CITY
HOLBROOK
CITY OP INDUSTRY
MACEDONIA
VENTURA
GARLAND
BRONX
SAM LEAMDRO
NEOOESHA
CARDENA
HOLLAND
ATLANTA
MARIETTA
ADA
SMYRNA
TOTOUA
WEST ROXBURY
NILES
PHILADELPHIA
CLIFTON
EAST BUTLER
RIVERSIDE
COLUMBUS
FAIRLAWN
CRAWFORD
NEW YORK
FRANKLIN
MARIETTA
CHICAGO
ST. LOUIS
COLLECEVILLE
NEW CASTLE
CRAMBURY
JOPPA
ALBION
MAY WOOD
Ull MINI: TUN
STATE
IN
PA
HI
HA
CA
OH
CA
TX
NY
CA
KS
CA
MI
CA
GA
MI
CA
NJ
MA
IL
PA
NJ
PA
CA
OH
NJ
NJ
NY
KY
OH
IL
MO
PA
IN
NJ
Ml)
IL
II.
in:
LATITUDE
41*100
401100
423000
420900
340200
411900
341700
333000
40)100
374400
372500
335300
424700
334500
335700
425900
335300
405400
421700
420200
395700
405200
405300
335900
395*00
405600
404000
404500
364300
392500
415200
383700
401100
395500
401900
392600
18^ 100
4 1 '. UK)
!')l SHU
LONGITUDE
855(00
750(00
882000
710100
1175600
.813100
1191(00
941700
715400
1220900
954100
1181(00
860700
842100
841100
851000
841100
741100
710900
874(00
751000
740900
795100
1172200
81OOOO
740000
741800
735700
861500
812700
873900
901200
752800
852200
743100
IbliOO
8HOUHI
M/ ••lull
r> i HID
PRODUCT CODE
A,C,D,F,K
A,B,C,O.E.F,H,I
A.C.D.E.F.K
C.D.E.G
A.B.C.D.G.H.K
A.C.D.E.F
A.C.D.E.H
A.D.F.K
C.D.E
A.D.F.K
A,D.C,E,G,I,K
A.D
A.C.D.E.K
C.D.E.C.H
A.C, D.C.I
A.D
A.C.C
A.C.C
r
G
A.C.D.E.F.C.K
A.D.E.F
i: , i> . c. . ii . K
A.D
A K
REFERENCE
1,1,4
3
3.6
3
3.*. 5
1.9
3
3
3
4.9
1
5
1
6
1,6.9
5
5
1.9
2,1.9
2,9
1
5
8
3,*
7
4
5.6
5
1.9
5
3
6.9
3
5
i
J.'>
1. '>
*• '*
-,
-------
NATIONAL LIST OF AEROSOL PACKAGERS (JULY 1987)
n
40
41
42
41
44
45
46
47
49
50
51
52
51
54
55
56
57
58
59
to
tl
62
tl
64
65
66
67
68
69
70
71
72
71
74
7S
It,
II
IB
COMPANY
CHEHSCOFE CORP.
CHEMSICO, INC.
CHEMSPRAY. INC.
CHEMTRONICS
CHEM-PACKAGING CORP.
CHEH-PAK. INC.
CHEN-TECH, LTD.
CHESEBROUCR-PONDS, INC.
d *»•> I RtfMISTB I ES fVRBiP
wUWr BBWUBlBBftKa lAJBrnT *
CLAYSON. INC. (GEM, INC. )
CLINE-BUCKNER, INC.
CONNECTICUT AEROSOLS, INC.
CONTACT INDUSTRIES, INC.
CONTINENTAL LABORATORIES. INC.
CPC-1 (PETERSON/PURITAN, INC.)
CPC 2 (PETERSON/PURITAN, INC.)
CPC-1 (PETERSONfPURITAN. INC.)
CRC CHEMICALS
CREATIVE PRODUCTS CORP.
CROWN INDUSTRIAL PRODUCTS CO.
CUSTOM-PAX PRODUCTS, INC.
C.S.A. LIMITED, INC.
DELCOR LABORATORIES, INC.
DEHERT I DOUGHERTY. INC.
DESOTO. INC.
DEVOE I RAYNOLDS
DYHON. INC.
EHBALMERS SUPPLY CO.
ENTERPRISE SALES CO.
ESKA PACKAGING CORP.
EVEREADY PRODUCTS CORP.
E.J. MCKERHAN CO.
FASSE PAINT co , INC
FAULTLESS STARCH (BON AMI CO.)
FLUID PACKAGING co . INC
FORREST PAINT co
FRANK OHI.ANDI . INC
FRANKLIN Oil. CUKH (HICOI. I>IV )
FULTON CO
CITY
ARLINGTON
ST. LOUIS
TOTOWA
HAUPPACE
POMPANO BEACH
WINCHESTER
DES KOINES
GREENWICH
POTOMAC
BYHALIA
ARTESIA
MILPORO
ELIZABETH
MADRID
CUMBERLAND
DANVILLE
ENGLEWOOD CLIFFS
WARMINSTER
NEW HAVEN
HEBRON
CERMANTOWH
HOUSTON
E. STROUDSBERG
OAK BROOK
DES PLAINES
LOUISVILLE
KANSAS CITY
WESTPORT
LOS ANGELES
LAKEWOOD
CLEVELAND
GARDEN GROVE
SHEBOYGAN FALLS
KANSAS CITY
LAKEWOOD
EUGENE
HUSHING
CLEVELAND
MIMTEH
STATE
TX
MO
NJ
NY
PL
VA
IA
CT
IL
MS
CA
CT
NJ
IA
RI
IL
•J
PA
CT
IL
WI
TX
PA
IL
IL
KY
KS
CT
CA
NJ
OH
CA
WI
MO
NJ
OR
NY
Oil
sc
LATITUDE
12*400
383700
405400
405OOO
261400
' 391100
413500
401800
345200
235200
411400
404000
415100
415700
400BOO
405100
401200
411800
6228OO
411400
294600
410000
415100
420300
181 50O
390700
410900
340400
400600
* 13000
31*700
43421)0
190600
400600
440SOO
4O4SOO
41 3UUO
iTi-illll
LONGITUDE
970700
•
901200
741100
731200
•00800
781000
911700
•74800
•94100
11*0500
710400
741100
914900
712500
•71700
715700
750600
755500
••2600
••0600
952200
751100
•75800
875200
854600
941BOO
732200
1181500
741300
814200
1175500
87*500
9*1500
7*1100
1230400
734900
Bit 200
Hl>/|im
PRODUCT CODE
A.B.D.F
A.C.D.E, F.I
A.C.D.C.H.I K
A.D.E. C.H
A.C.D.E
A.B.D.F
E.I
A.B.C.D.G.K
C.D.G
C.D.E
A.C.D.E.F.C.B.I
A. C.D.E, C.B.I
c.c
A.B.C.D.E.C.B.I.K
A.t.C.D.C.H.K
D.F
D.F
A.C.D.E.C I
G.B
A.C.D.C.K
A.D.E
D.E.K
A.D.E
A.C.D.F.K
F
C.H
C.II.K
1)
K
REFERENCE
3,9
1.9
3
3.9
3
3.6,9
3
5
1
1.1.8,9
3
3.9
3.4.9
1
6
4.6
6
6
3
3.6,9
J.s
1
1
1,3,9
i
i
1.5
5
3
1
3,i
*.a
}
i
*.9
•)
1
b.t
)
-------
NATIONAL LIST OF AEROSOL PACKAGERS (JUl.V 1987)
80
• 1
•2
• 3
84
83
86
• 7
88
a*
90
91
92
91
94
95
96
97
98
99
too
101
102
101
10*
105
106
107
108
109
110
111
112
113
111
115
1 16
1U
1 IB
COMPANY
CEHINI AEROSOLS, INC.
GEMINI LACQUERS
GEM. INC.
GENERAL PAINT
GEORGIA PACIFIC CORP.
CILETTE CO.
CLIODEN PAINTS
GROW CROUP- 1 (CELLO CORP.)
GROU CROUP- 2 (NATIONAL AEROSOL PRODUCTS)
GUARDSMAN (AMERICAN AEROSOL INC.)
GUEST PACKAGING
HOLT LLOYD (LPS PRODUCTS)
HOWARD JOHNSON
HYDROSOL
HVSAN CORP.
IKI MFC CO.
ILLINOIS IRONZE PAINT CO.
JET-AER CORP.
JL MFC.
KNIGHT OIL CORP.
KONALRAD PRODUCTS. INC.
LAHAUR COMPANY
LAURENCE-NCrADDEN CO.
LAUSON CHEMICAL PRODUCTS CO. .
MARCY LABS
H8L INDUSTRIES. INC.
METROVAL, INC. (EPIC INDUSTRIES. INC.)
MIOCO PRODUCTS, CO
MOIILE PAINT
MOHAWK FINISHING
MOHAWK LABORATORIES
MORTON PHARMACEUTICALS, INC.
NATIONWIDE INDUSTRIES
NEW ENGLAND AEROSOL I PACKAGING CORP.
NEU YORK BRONZE 1
HtU YORK BRONZE 2
NORTHEAST PACKAGING INC
NOXEI.L. IMC.
OAKITE PKOIlUCTS-1 (CI.AIRt. MHi CO )
CITY
EL RENO
BEVERLY
BYHALIA
GARY
ATLANTA
ANDOVER
CLEVELAND
SANTA FE SPRINGS
CERRITOS
HOLLAND
RABWAY
TUCKER
NORTH qUINCY
BURR RIDGE
CHICAGO
EDCERTOH
LAKE ZURICH
PATERSON
CRANBURY
JOHNSTOWN
PANDORA
MINNEAPOLIS
PHILADELPHIA
TORRANCE
ADDISON
SANTA ANA
HETUCHEH
MARYLAND HEIGHTS
THEODORE
AMSTERDAM
IRVING
MEMPHIS
PANDORA
WOBURN
ELIZABETH
TAYLOR
ORANGE
BALTIMORE
ADD I SON
STATE
OK
HA
MS
IL
CA
MA
Oil
CA
CA
MI
NJ
CA
MA
IL
IL
HI
IL
NJ
TX
NY
OH
MM
FA
CA
IL
CA
NJ
HO
AL
NY
TX
TN
OH
MA
NJ
PA
CT
Ml)
IL
LATITUDE
353200
423100
343200
421300
334500
424000
413000
33S700
33S200
424700
403700
335100
421700
414700
413200
425000
411200
405500
332700
. 430000
405700
445900
393700
335000
415600
334600
403200
384300
303300
424600
324900
350800
405700
422900
404000
412200
111 JOU
J9I7OO
llbbUU
LONGITUDE
975700
705300
884100
881400
842300
710800
814200
1180400
1180500
860700
741600
841300
710100
8755OO
873900
890400
880500
741100
974700
742200
835800
931600
751000
1181900
875900
1175200
742200
902600
881000
741100
965600
900300
835800
710900
141)00
754300
730200
J61/OO
B/VKll)
PRODUCT CODE
A,F,
C,D,G
A.C,D,E,F,C,I,K
C,G
D
A.C.D.E.F.K
A,C,D,E,F,C,K
A,C,D,E,G,I,H,K
A.D.F.K
A.C.D.E.I.K
A,C,D,F
A,C,D,P
A.D.E.F
A,C,I,K
A,C,D,E,K
A.C.D.E.F.I
A, C, D.F.I
A.C,D,E,F,G,K,I
F
A . C , I) , E . ¥ , (. , II
A.I:. II K
REFERENCE
3
5
3
5
5
6
6
5 .
2.7.9
1.3.3.9
3
6,7
5
3.5
3
1,3,9
1.3.9
I
3
3,9
3
6
7,»
3
1.3,9
3
5.9
3.9
5
S
S
3.9
a
3.5
5,6
6
1
•>
\ . v» . •*
-------
NATIONAL LIST OF AEROSOL PACKAGERS (JULY 1987)
120
121
122
121
12*
125
12*
127
121
12t
110
111
112
111
114
115
11*
117
Hi-
nt
1*0
1*1
1*2
1*1
1*4
1*}
l*t
1*7
!*•
1*»
ISO
lil
142
153
IS*
155
156
Ii7
Ib8
COMPANY
OAKITE PRODUCTS -J
-------
NATIONAL LIST OF AEROSOL PACKAGERS (JULY 198?)
160
161
162
16)
164
165
166
167
161
169
170
171
172
17)
174
175
176
177
17t
179
110
111
112
11)
114
115
116
It?
Ill
119
190
COMPANY
SPRAY PRODUCTS CORP.
SSP CHEMICAL CO.. INC.
STALFORT CONSUMER PRODUCTS
STANDARD BRANDS PAINT CO.
STANHOME. INC.
STAR CHEMICAL CO.. INC.
SIGNERS INK CO.
STROBEL PRODUCTS. INC.
SUN LABS-1 (SOUTHEAST PACKAGING CO. I
SUN LAIS -2
TALLEV INDUSTRIES (TIKE HIST INC.)
TECH LUBE
TECBNAIR LAIS. INC.
TESTOR CORP
TBEOCHEN LABORATORIES. INC.
)M CO.
TRIMARK PACKAGING. INC.
ULTRAHDTIVE CORP
UNCOMMON CONGLOMERATES
UN I PACK, INC.
UNIVERSAL SPECIALTY PACKAGING
US AVIEX CO.
US PACKAGING CORP
VALJEAN CORP.
VICTOR INDUSTRIES CORP
WHITMIRE RESEARCH
WILLIAM BARK i CO.
IEP MANUFACTURING CO.
IIP AEROSOL PRODUCTS
ZOE CHEMICAL CO., INC.
ZYNOLYTE PRODUCTS CO.
CITY
HORRISTOUN
ROYERSFORD
HAVRE DE GRACE
TORRANCE
HESTFIELD
BINSDALE
QUARRYVILLE
LOUISVILLE
ATLANTA
CHATSMORTB
UATERBURY
I SLIP
RAHUAY
ROCKFORD
TAMPA
ST. PAUL
ENNIS
BETHEL
ST. PAUL
PITTSBURGH
ROSELLE
NILES
WHEELING
INDIAN HARBOUR BEACH
CHICO
ST. LOUIS
MEMPHIS
ATLANTA
CANOCA PARK
NEW HYDE PARK
COMPTON
STATE
PA
PA
MD
CA
MA
IL
PA
KY
GA
CA
CT
NY
NJ
IL
PL
MN
TX
VI
MN
PA
NJ
MI
IL
PL
CA
MO
TN
CA
CA
NY
CA
LATITUDE
400700
401100
393300
335000
420700
414100
305400
3*1500
3)4500
341500
413300
404400
40)700
411500
275700
445700
322000
4)5000
445700
402600
404000
415000
420100
210900
394400
31)700
350800
3)4500
)41200
404400
335*00
LONGITUDE
752100
75)300
760600
1111900
724500
•75600
761000
154600
•42)00
111)600
7)0)00
7)1)00
741600
•75100
•22700
9)0600
96)100
72)100
9)0600
•00100
741500
•61500
•75500
•0)600
1215000
901200
900)00
8*2)00
118)500
73*100
1181300
PRODUCT CODE
A.D.E.F
C.D.E.F
A.C.D.E
A.C.D.E.C
F,D
A.C.D.F
A.C.E.G.K
G
E
A.C.D.H
A.C.D.C.K.I
A.C.D.E.F.C.H.l
B.G.H.K
A.C.O.E
A.C.D.F.K
C.E.C.H.I
A, 8, C.D.E.F, C.H.I, 1C
D.E
C, D.E.I
REFERENCE
3.9
3
3
1.9
2.3.8.9
3.5
5
3.9
4.5
3.5
2,9
6.9
4
5
•
3.6
4
3.8
6
3
).s
3
3
3
3
6
3
5,6,9
6.9
3,4.8
7
-------
o
NATIONAL LIST OF AEROSOL PACKAGERS (JULY 1987)
COMPANY CITY
STATE LATITUDE LONGITUDE PRODUCT CODE REFERENCE
PACKAGING FACILITIES WITH UNIDENTIFIED LOCATION
1*1
192
191
19*
m
19*
1*1
191
199
200
201
202
20}
20*
20S
206
20?
201
209
210
211
212
AEROSOL SPECIALTIES
AMERICAN JET WAY
CESSCO. INC.
CHEMICAL PACKAGING SERVICES. INC.
CHEMI -COATINGS, INC.
C.P. BURGER
EHKO CO.
ro-MO PRODUCTS
IC-LO PRODUCTS CORF.
1NTERDYNAMICS. INC.
JIM YORK CHEMICALS CO.
HACNA/LUX CORP.
MAJOR PAINT
MILLER-STEPHEN SOM
NELSON PAINT
PETRO CHEMICAL PRODUCTS
SHIELD CHEMICAL CO.
SHIRLO, INC.
TECH SPRAY
TECHNICAL CHEMICALS
TRADCO
UNITED COATINGS
5
5
S
5
i
5
1
5
S
5
1
5
1
S
S
i
i
5
J
J
5
S
PRODUCT CODE:
A - AUTOMOTIVE
R - FOOD
C - HOUSEHOLD
D - INDUSTRIAL
E - INSECTICIDE
F • PAINT
G - PERSONAL
H - PHARMACEUTICAL
I - VETERINARY
K - SPECIALTY
REFERENCE:
1 - STANDARD AMD POOR'S REGISTER. 1900
2 - CORPORATE AFFILIATIONS, 1986
3 - AEROSOL ACE BUYER'S CUIDK. OCTOBER 1986
« - AEROSOL AGE (1983 ISSUES)
S - CSMA PRESSURIZED PRODUCTS SURVEY. 1985
6 - EPA MEMORANDUM, DOCUMENTATION OF TELEPHONE COMMUNICATIONS CONCERNING
THE PACKAGING AND LOCALIZED LARGE-SCALE USERS OF AEROSOL PRODUCTS,
PREPARED BY GARY BOCKOL. RADIAN CORPORATION. FEBRUARY 6.19B/
7 - OCCUPATIONAL EXPOSURE AMD ENVIRONMENTAL ASSESSMENT OF FOUR CHLORINATED
SOLVENTS UHEN USED IN AEROSOLS, MARCH 28,1986
8 « CSMA VENDORS TO THE TRADE GUIDE. 1V86
9 - THOMAS REGISTER, 1«95
-------
APPENDIX D
TRIS LIST OF PHARMACEUTICAL FACILITIES USING METHYLENE CHLORIDE
D-l
-------
APPENDIX D
TRIS LIST OF PHARMACEUTICAL FACILITIES USING METHYLENE CHLORIDE
D-l
-------
Treatments for Methylene Chloride (CAS 000075092)
SIC THIS ID FACILITY NAME
WC
WTC
1C
STI
EFFIC
OD
O
K>
283 00617BBTTCROADN
283 00617BBTTCROADN
283 O0617BBTTCROADN
283 OO617MRCKSSTATB
283 O0617MRCKSSTATE
283 00617MRCK6STATE
283 00617MRCKSSTATE
283 00617HRCKSSTATE
283 00617PFZRPHIGHW
283 00617PFZRPHIGHW
283 00617PFZRPHIGHW
283 00617PFZRPHIGHW
283 00617THPJHHIGHW
283 00628LLLLY65THI
283 00628LLLLY65THI
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATB
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATR
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00661SQBBMSTATE
283 00671KYPHRPRIDC
283 00671KYPHRPRIDC
283 00671KYPHRPRIDC
283 00671KYPHRPRIDC
283 00671KYPHRPRIOC
283 00671KYPHRPRIOC
283 OO671KYPHRPRIOC
283 00671KYPHRPRIDC
283 00671KYPHRPRIOC
283 00701RCHPRSTATE
283 00701RCHPRSTATE
ABBOTT CHEMICALS INC.
ABBOTT CHEMICALS INC.
ABBOTT CHEMICALS INC.
MERCK SHARP & DOHME QUIMICA DE
MERCK SHARP & DOHME QUIMICA DE
MERCK SHARP & DOHME QUIMICA DE
MERCK SHARP & DOHME QUIMICA DE
MERCK SHARP & DOHME QUIMICA DE
PFIZER PHARMACEUTICALS INC.
PFIZER PHARMACEUTICALS INC.
PFIZER PHARMACEUTICALS INC.
PFIZER PHARMACEUTICALS INC.
UPJOHN MFG. CO.
ELI LILLY INDUSTRIES INC.
ELI LILLY INDUSTRIES INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SQUIBB MFG. INC.
SCHERING-PLOUGH PRODUCTS INC.
SCHERING-PLOUGH PRODUCTS INC.
SCHERING-PLOUGH PRODUCTS INC.
SCHERING-PLOUGH PRODUCTS INC.
SCHERING-PLOUGH PRODUCTS INC.
SCHERING-PLOUGH PRODUCTS INC.
SCHERING-PLOUGH PRODUCTS INC.
SCHERING-PLOUGH PRODUCTS INC.
SCHERING-PLOUGH PRODUCTS INC.
ROCHE PRODUCTS INC.
ROCHE PRODUCTS INC.
P.R.
P.R.
P.R.
: P.R.
! P.R.
.
.
KEY PHARMA
KEY PHARMA
KEY PHARMA
KEY PHARMA
KEY PHARMA
KEY PHARMA
KEY PHARMA
KEY PHARMA
KEY PHARMA
A
A
A
L
A
A
A
A
W
A
L
A
A
A
A
A
A
A
A
A
W
L
H
L
A
A
A
W
L
H
A
A
H
W
L
L
L
L
L
A
H
P21
Bll
A02
F01
A03
A02
A02
A02
Cll
A03
Fll
A02
A03
Pll
NA
A02
A02
A03
A04
A02
A03
F01
F01
Bll
Rll
A02
A02
A03
F01
F01
Bll
P12
P21
P42
P19
R13
Rll
P01
Bll
P12
P21
P01
3
3
1
1
1
1
1
2
2
2
2
2
2
NA
1
1
1
1
1
3
1
3
1
1
1
1
4
1
3
1
2
4
1
3
Y
¥
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
O8SOO
09500
09800
00000
10000
OBOOO
07100
07250
OOOOO
07300
10000
10000
O2000
05400
NA
09000
O9500
O9500
09500
OOOOO
O9400
10000
10000
09800
O9000
O9000
O9SOO
O9000
10000
10000
09800
OOOOO
O9800
09800
09800
09800
09900
OOOOO
09500
OOOOO
06000
OOOOO
N
N
N
Y
N
N
N
N
N
Y
Y
N
Y
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
Y
Y
Y
Y
N
Y
Y
N
-------
Treatments for Methylene chloride (CAS 000075092)
SIC TRIS ID FACILITY NAME
WC
WTC
1C
STI
EFFIC
OD
o
283 00701RCHPRSTATE
283 00701RCHPRSTATE
283 00701RCHPRSTATE
283 00701RCHPRSTATE
283 00701SCHRNROAD6
283 00732BLCHMRDN01
283 00732BLCHMRDNO1
283 06340PFZRNEASTE
283 06340PFZRNEASTE
283 06340PFZRNEASTE
283 06340PFZRNEASTE
283 06340PFZRNEASTE
283 06810DNBRY131WE
283 07072RSYNCFOOTO
283 07072RSYNCFOOTO
283 07072RSYNCFOOTO
283 07072RSYNCFOOTO
283 07080NTRLB650SO
283 07083SCHRN1011M
283 07083SCHRN1011M
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HPFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07110HFFMN340KI
283 07424MDPHR101EM
283 07463BCRFT12IND
283 07901CBGGY556MO
283 07901CBGGY556MO
283 07901CBGGY556MO
ROCHE PRODUCTS INC.
ROCHE PRODUCTS INC.
ROCHE PRODUCTS INC.
ROCHE PRODUCTS INC.
SCHERING INDUSTRIAL DEVELOPMENT CORP.
BILCHEM LTD.
BILCHEM LTD.
PFIZER INC. GROTON SITE
PFIZER INC. GROTON SITE
PFIZER INC. GROTON SITE
PFIZER INC. GROTON SITE
PFIZER INC. GROTON SITE
DANBURY PHARMACAL INC.
ARSYNCO INC.
ARSYNCO INC.
ARSYNCO INC.
ARSYNCO INC.
NUTRO LABORATORIES INC.
SCHERING CORP.
SCHERING CORP.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.
HOFFMANN-LA ROCHE INC.'
AMIDE PHARMACEUTICAL INC.
BIOCRAFT LABORATORIES INC.
CIBA-GEIGY CORP. PHARMACEUTICALS DIV.
CIBA-GEIGY CORP. PHARMACEUTICALS DIV.
CIBA-GEIGY CORP. PHARMACEUTICALS DIV.
W
W
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N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
Y
-------
Treatments for Methylene Chloride (CAS O00075092)
SIC THIS ID FACILITY NAME
WC
WTC
1C
STI
EFFIC
00
D
283 07901CBGGY5S6MO
283 07901CBGGY556MO
283 07936SDMKL17WES
283 07936SNDZP59ROU
283 08807MRCNCEASTM
283 08807MRCNCEASTM
283 08807MRCNCEASTM
283 08807MRCNCEASTM
283 08807MRCNCEASTM •
283 08854BCHML101PO
283 08854BCHML101PO
283 08876HCHSTRTE20
283 08902RSQBBONESQ
283 06902RSQBBONESQ
283 06902RSQBBONESQ
283 08902RSQBBONESQ
283 10901CBG6YOLDMI
283 10920PRPHR75BRE
283 10965LDRLLNORTH
283 11S90TSHCN125ST
283 12979YRSTL64MAP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 13221BRSTLTHOMP
283 14623PNNWL755JE
283 14623PNHWL755JB
283 14623PNNWL755JB
283 15147PNNXPEASTB
283 17868MRCKC100AV
283 17868MRCKC100AV
283 17868MRCKC100AV
283 17868MRCKC100AV
283 17868MRCKC100AV
CIBA-GEIGY CORP. PHARMACEUTICALS DIV.
CIBA-GEIGY CORP. PHARMACEUTICALS DIV.
SIDHAK LABORATORIES INC.
SANDOZ PHARMACEUTICALS CORP.
LEDERLE LABORATORI
LBDERLE LABORATORI
LEDERLE LABORATORI
LEDERLE LABORATORI
LEDERLE LABORATORI
AMERICAN CYANAMID CO.
AMERICAN CYANAMID CO.
AMERICAN CYANAMID CO.
AMERICAN CYANAMID CO.
AMERICAN CYANAMID CO.
SMITHKLINE BEECHAM PHARMACEUTICALS
SMITHKLINE BEECHAM PHARMACEUTICALS
HOECHST CELANESE CORP. LIFE SCIENCES
E.R. SQUIBB £ SONS
B.R. SQUIBB 6 SONS
E.R. SQUIBB ft SONS
B.R. SQUIBB & SONS
CIBA-GEIGY CORP. PHARMACEUTICALS DIV.
,PAR PHARMACEUTICAL INC.
LEDERLE LABORATORIES
TISHCON CORP.
AYBRST LABORATORIES INC.
BRISTOL-MYERS SQUIBB CO. INDUSTRIAL DIV.
BRISTOL-MYERS SQUIBB CO.
BRISTOL-MYERS SQUIBB CO.
BRISTOL-MYERS SQUIBB CO.
BRISTOL-MYERS SQUIBB CO. INDUSTRIAL DIV.
BRISTOL-MYERS SQUIBB CO. INDUSTRIAL DIV.
BRISTOL-MYERS SQUIBB CO. INDUSTRIAL DIV.
BRISTOL-MYERS SQUIBB CO. INDUSTRIAL DIV.
BRISTOL-MYERS SQUIBB CO.
BRISTOL-MYERS SQUIBB CO.
BRISTOL-MYERS SQUIBB CO.
FISONS CORP.
FISONS CORP.
FISONS CORP.
PENNEX PRODUCTS CO. INC.
MERCK & CO. INC.
MERCK & CO.
MERCK & CO.
INDUSTRIAL DIV.
INDUSTRIAL DIV.
INDUSTRIAL DIV.
INDUSTRIAL DIV.
INDUSTRIAL DIV.
INDUSTRIAL DIV.
MERCK & CO.
MERCK & CO.
INC.
INC.
INC.
INC.
H
L
A
H
A
W
A
A
A
A
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1
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2
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N
Y
N
Y
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
Y
Y
-------
Treatments for Methylene Chloride (CAS 000075092)
SIC TRIS ID FACILITY NAME
WC
WTC
1C
STI
EFFIC
OD
a
ui
283 1786SMRCKC100AV
283 17868MRCKC100AV
283 19034RRRPH500VI .
283 19130SMTHK1500S
283 19130SMTHK1500S
283 19130SMTHK1500S
283 19382FRMNT510EU
283 19382FRMNT510EO
283 19382HYTHY611EN
283 19382WYTHY611EN
283 19382WYTHY611EN
283 19382 WYTHY6 HEN
283 19382WYTHY6HEN
283 19382WYTHY611EH
283 19428SMTHK900RI
283 19428SMTHK900RI
283 19428SMTHK900RI
283 19428SMTHK900RI
283 19801NRMCF5000L
283 2122SKNSCL6118R
283 21225KNSCL6118R
283 23805LLBRT2999F
283 23805LLBRT2999F
283 23805LLBRT2999F
283 275970LXNC1011N
283 27597GLXNC1011N
283 27597GLXNC1011N
283 27597GLXNC1011N
283 27835BRRGHINTER
283 27835BRRGHINTER
283 27835BRRGHINTER
283 27835BRRGHINTER
283 27835BRRGHINTER
283 31708MRCKC3517R
283 31708MRCKC3517R
283 31708MRCKC3517R
283 31708MRCKC3517R
283 31708MRCKC3517R
283 37620BCHMLINDUS
283 37620BCHMLINDUS
283 45215MRRLL2110E
MERCK 6 CO. INC.
MERCK & CO. INC.
RHONE-POULENC RORER PHARMACEUT ICAL INC.
SMITHKLINE BEECHAM PHARMACEUTICALS
SMITHKLINE BEECHAM PHARMACEUTICALS
SMITHKLINE BEECHAM PHARMACEUTICALS
FERMTEC PRODUCTS INC.
FERMTEC PRODUCTS INC.
WYETH-AYERST LABORATORIES INC.
WYETH-AYERST LABORATORIES INC.
WYETH-AYERST LABORATORIES INC.
WYETH-AYERST LABORATORIES INC.
'WYETH-AYERST LABORATORIES INC.
WYETH-AYERST LABORATORIES INC.
SMITHKLINE BEECHAM PHARMACEUTI CALS
SMITHKLINE BEECHAM PHARMACEUTI CALS
SMITHKLINE BEECHAM PHARMACEUTI CALS
SMITHKLINE BEECHAM PHARMACEUTI CALS
NORAMCO OF DELAWARE INC.
KANASCO LTD.
KANASCO LTD.
LEE LABORATORIES INC. & INFRACORP LTD.
LEE LABORATORIES INC. £ INFRACORP LTD.
LEE LABORATORIES INC. 6 INFRACORP LTD.
GLAXO INC. TECHNICAL OPERATIONS DIV.
GLAXO INC. TECHNICAL OPERATIONS DIV.
GLAXO INC. TECHNICAL OPERATIONS DIV.
GLAXO INC. TECHNICAL OPERATIONS DIV.
BURROUGHS WELLCOME CO.
BURROUGHS WELLCOME CO.
BURROUGHS WELLCOME CO.
BURROUGHS WELLCOME CO.
BURROUGHS WELLCOME CO.
MERCK & CO. INC. FLINT RIVER PLANT
FLINT RIVER PLANT
FLINT RIVER PLANT
FLINT RIVER PLANT
FLINT RIVER PLANT
MERCK & CO.
MERCK £ CO.
MERCK & CO.
INC.
INC.
INC.
MERCK & CO. INC.
BEECHAM LABORATORIES
BEECHAM LABORATORIES
MBRRELL DOW PHARMACEUTICALS
INC.
A
A
A
A
W
W
W
W
W
W
W
W
W
A
A
W
W
A
A
W
A
L
L
A
W
W
W
W
S
A
W
A
A02
A02
NA
F71
A03
NA
Bll
Bll
P01
Bll
P14
P01
Bll
P14
F01
A02
A03
NA
NA
NA
NA
PIS
Cll
A03
A02
A04
Cll
A02
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F01
A03
P01
Cll
Bll
Pll
P13
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A03
A03
2
2
2
3
3
3
3
2
1
2
NA
4
3
1
2
1
1
1
2
1
1
2
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
08300
09100
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08690
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Y
N
N
N
N
Y
N
N
N
N
N
N
N
N
N
Y
N
N
N
N
-------
Treatments for Methylene
SIC TRIS ID
283 45215MRRLL2110E
283 46285LLLLY1555K
283 46285LLLLY1555K
283 46285LLLLYLILLY
283 46285LLLLYLILLY
283 46285LLLLYLILLY
283 46285LLLLYLILLY
283 46285LLLLYLILLY
283 47721BRSTL2404P
283 47721BRSTL2404P
283 47842LLLLYSTATB
283 47842LLLLYSTATB
283 47842LLLLYSTATE
283 47842LLLLYSTATE
283 47842LLLLYSTATE
283 47842LLLLYSTATE
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 47905LLLLYLILLY
283 49001THPJH7171P
283 49001THPJH7171P
283 49001THPJH7171P
283 49001THPJH7171P
283 49001THPJH7171P
283 49001THPJH7171P
283 49001THPJH7171P
283 49001THPJH7171P
283 49001THPJH7171P
Chloride (CAS 000075092)
FACILITY NAME
MERRELL DOW PHARMACEUTICALS INC.
WC
WTC
1C
STI
EFFIC
OD
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
MEAD JOHNS N
MEAD JOHNS N
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY
ELI LILLY £ CO.
ELI LILLY £ CO.
UPJOHN CO.
UPJOHN CO.
UPJOHN CO.
UPJOHN CO.
UPJOHN CO.
UPJOHN CO.
UPJOHN CO.
UPJOHN CO.
UPJOHN CO.
CO. LILLY INDUSTRIAL CENTER
CO. LILLY INDUSTRIAL CENTER
CO. LILLY CORPORATE CENTER
LILLY CORPORATE CENTER
LILLY CORPORATE CENTER
LILLY CORPORATE CENTER
LILLY CORPORATE CENTER
fi CO. EVANSVILLE PLANT
£ CO. EVANSVILLB PLANT
CO. CLINTON LABORATORIES
CO. CLINTON LABORATORIES
CLINTON LABORATORIES
CLINTON LABORATORIES
CLINTON LABORATORIES
CO. CLINTON LABORATORIES
CO. TIPPECANOE LABORATORIES
TIPPECANOB LABORATORIES
TIPPECANOE LABORATORIES
TIPPECANOE LABORATORIES
TIPPECANOB LABORATORIES
TIPPECANOB LABORATORIES
TIPPECANOB LABORATORIES
TIPPECANOB LABORATORIES
TIPPECANOB LABORATORIES
TIPPECANOB LABORATORIES
TIPPECANOB LABORATORIES
TIPPECANOB LABORATORIES
CO. TIPPECANOB LABORATORIES
CO. TIPPECANOB LABORATORIES
TIPPECANOE LABORATORIES
TIPPECANOB LABORATORIES
PRODUCTION FACILITY
PRODUCTION FACILITY
PRODUCTION FACILITY
PRODUCTION FACILITY
PRODUCTION FACILITY
PRODUCTION FACILITY
PRODUCTION FACILITY
PRODUCTION FACILITY
PRODUCTION FACILITY
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
CO.
A
A
A
L
A
A
W
L
A
A
L
A
A
W
H
L
L
H
W
S
H
H
H
L
A
L
L
L
L
A
A
A
A
NA
A02
NA
A07
A03
R12
A02
NA
A03
NA
F01
F01
F71
A02
Rll
NA
A02
A03
Bll
Cll
F01
P01
P01
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P13
F01
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P42
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P21
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NA
R13
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NA
A02
NA
1
NA
3
3
1 Y
NA Y
NA
2
1
1
1
1
1
NA
1
1
3
3
1
1
3
3
3
2
3
1
1
1
1
NA
1
1
2
1
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NA Y
NA
1
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10000
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10000
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09900
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08000
NA
N
N
N
N
N
N
N
N
N
N
N
N
Y
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
-------
Treatments for Methylene Chloride (CAS 000075092)
SIC TRI8 ID FACILITY NAME
WC
WTC
1C
STI
EFFIC
OD
283 49424PRKDV188HO
283 49424PRKDV188HO
283 49424PRKDV188HO
283 49424PRKDV188HO
283 55447PSHRS14905
283 56623RDRWL210MA
283 60064BBTTL1400N
283 60064BBTTL1400N
283 60077GDSRL4901S
283 60077GDSRL4901S
283 60915RMRPHRT50A
283 63141KVPHR2303S
283 64137MRNLBMARIO
283 65807SYNTX2460W
283 65807SYNTX2460W
283 68521NRDNL601HE
283 80020CRDLB2555H
283 80301HSRCH4750N
283 80301SYNTX2075N
283 80301SYNTX2075N
283 803018YNTX207SN
283 80301SYNTX2075N
283 80301SYNTX2075N
283 85260NTRLL14810
283 90505BCHMH3132K
283 91324MRKR 19901
283 92121MLTPL3550G
283 92713NBLCN17802
283 94303LZCRP2575H
283 94303LZCRP2575H
283 95688LZCRP700EU
PARKE-DAVIS DIV. OF WARNER-LAMBERT CO.
PARKE-DAVIS DIV. OF WARNER-LAMBERT CO.
PARKE-DAVIS DIV. OF WARNER-LAMBERT CO.
PARKE-DAVIS DIV. OF WARNER-LAMBERT CO.
UPSHER-SMITH LABORATORIES INC.
RBID-ROWELL INC.
ABBOTT LABORATORIES
ABBOTT LABORATORIES
G. D. SEARLE C CO.
G. D. SEARLE fc CO.
ARMOUR PHARMACEUTICAL CO.
KV PHARMACEUTICAL CO.
MARION MERRELL DON INC. MARION PARK
SYNTEX AGRIBUSINESS INC.
SYNTEX AGRIBUSINESS INC.
SMITHKLINE BEECHAM ANIMAL HEALTH
GENEVA PHARMACEUTICALS INC.
HAUSER CHEMICAL RESEARCH INC.
SYNTEX CHEMICALS INC.
SYNTEX CHEMICALS INC.
SYNTEX CHEMICALS INC.
SYNTEX CHEMICALS INC.
SYNTEX CHEMICALS INC.
NATURALLY VITAMIN SUPPLEMENTS INC.
BACHEM INC.
3M RIKER
MULTIPLE PBPTIDB SYSTEMS L.P.
ANABOLIC INC.
ALZA CORP.
ALZA CORP.
ALZA CORP.
w
s
A
L
W
A
A
A
W
A
L
A
A
A
W
L
A
A
A
A
P01
P12
F71
Rll
NA
NA
Bll
A02
A02
NA
NA
A07
NA
P41
A03
NA
NA
Rll
A03
A04
A04
Bll
NA
NA
NA
NA
Rll
P41
F71
A03
A02
3
3
1
1
2
1
1
NA
3
3
2
1
2
NA
2
2
NA
1
2
1
1
ooooo
00000
09999
09500
OOOOO
OOOOO
0993O
09500
07000
NA
OOOOO
OOOOO
OOOOO
0800O
00300
OOOOO
OOOOO
09600
Y NA
Y 0050O
OOOOO
09600
NA
OOOOO
OOOOO
OOOOO
08300
00130
Y NA
Y 10000
0930O
N
N
Y
N
Y
N
N
N
Y
N
N
Y
N
N
N
N
N
N
N
Y
Y
-------
Emissions of Methylene Chloride (CAS 000075092) I
13:44 Tuesday, May 5, 1992
SIC-283
SIC THIS ID
283 85260NTRLL14810
283 37620BCHMLINDUS
283 14623PNNWL755JE
283 15147PNNXPEASTE
283 06810DNBRY131WE
283 80020CRDLB2555W
283 19034RRRPH500VI
283 31708MRCKC3517R
283 23305LLBRT2999F
283 07080NTRLB650SO
283 07936SNDZP59ROU
283 00617MRCKSSTATE
283 55447PSHRS14905
283 12979YRSTL64MAP
FACILITY NAME
NATURALLY VITAMIN SUPPLEMENTS INC.
BEECHAM LABORATORIES
FISONS CORP.
PENNEX PRODUCTS CO. INC.
DANBURY PHARMACAL INC.
GENEVA PHARMACEUTICALS INC.
RHONE-POULENC RORER PHARMACEUT ICAL INC.
MERCK & CO. INC. FLINT RIVER PLANT
LEE LABORATORIES INC. & INFRACORP LTD.
NUTRO LABORATORIES INC.
SANDOZ PHARMACEUTICALS CORP.
MERCK SHARP & DOHME QUIMICA DE P.R.
UPSHER-SMITH LABORATORIES INC.
AYERST LABORATORIES INC.
LOCATION
SCOTTSDALE, AZ
BRISTOL, TN
ROCHESTER, NY
VERONA, PA
DANBURY, CT
BROOMFIELD, CO
FORT WASHINGTON, PA
ALBANY, GA
PETERSBURG, VA
SOUTH PLAINFIELD, NJ
EAST HANOVER, NJ
BARCELONETA, PR
MINNEAPOLIS, MN
ROUSES POINT, NY
ONSITE
02
04
04
03
03
03
06
04
03
04
04
03
04
FUGITIVE
EMISSIONS
0
0
250
1148
250
0
0
250000
51
0
93
650
0
250
FC
0
0
C
0
0
0
O
M
0
PARENT COMPANY
MARLYN CO.
SMITHKLINE BEECHAM PHARMACEUTI
FISONS CORP.
NV MEDICOPHARMA
HENRY SCHEIN INC.
CIBA GEIGY CORP.
RHONE-POULENC RORER INC.
MERCK & CO. INC.
BOEHRINGER INGELHEIM & A. H. R
NA
SANDOZ CORP.
MERCK & CO. INC.
NA
AMERICAN HOME PRODUCTS CORP.
TOTAL
EMISSIONS
100
184028
2266
141148
162250
14412
31367
1450000
7951
30000
2343
920
120000
16250
STACK
EMISSIONS
100
184028
2016
140000
162000
14412
31367
1200000
7900
30000
2250
270
120000
16000
SC
O
M
0
C
C
C
C
O
O
C
0
0
C
E
D-a
-------
Emissions of Methy1ene Chloride (CAS 000075092) 2
13:44 Tuesday, May 5, 1992
- SIC=283 -
(continued)
SIC TRIS ID
283 17868MRCKC100AV
283 06340PFZRNEASTE
283 07936SDMKL17WES
283 10920PRPHR75BRE
283 64137MRNLBMARIO
283 90505BCHMN3132K
283 68521NRDNL601WE
283 60915RMRPHRT50A
283 00701SCHRNROAD6
283 07424MDPHR101EM
283 65807SYNTX2460W
283 00617THPJHHIGHW
283 19382FRMNT510EU
FACILITY NAME
MERCK & CO. INC.
PFIZER INC. GROTON SITE
SIDHAK LABORATORIES INC.
PAR PHARMACEUTICAL INC.
MARION MERRELL DOW INC. MARION PARK
BACHEM INC.
SMITHKLINE BEECHAM ANIMAL HEALTH
ARMOUR PHARMACEUTICAL CO.
SCHERING INDUSTRIAL DEVELOPMENT CORP.
AMIDE PHARMACEUTICAL INC.
SYNTEX AGRIBUSINESS INC.
UPJOHN MFG. CO.
FERMTEC PRODUCTS INC.
LOCATION
RIVERSIDE, PA
GROTON, CT
EAST HANOVER, NJ
CONGERS, NY
KANSAS CITY, MO
TORRANCE, CA
LINCOLN, NE
BRADLEY, IL
MANATI, PR
LITTLE FALLS, NJ
SPRINGFIELD, MO
BARCELONETA, PR
WEST CHESTER, PA
PARENT COMPANY
MERCK & CO. INC.
PFIZER INC.
NA
NA
DOW CHEMICAL CO.
NA
SMITHKLINE BEECHAM CORP.
RHONE-POULENC RORER INC.
SCHERING INDUSTRIAL DEVELOPMEN
NA
SYNTEX USA INC.
UPJOHN CO.
BURNS PHILP & CO. LTD.
ONSITE
05
05
03
03
04
03
04
04
04
03
05
06
04
FUGITIVE
EMISSIONS
200000
17000
4395
200
750
5
5200
0
250
2192
31243
4995
0
FC
O
M
C
O
E
O
O
O
O
E
E
STACK
EMISSIONS
110000
8500
171398
1300
58000
250
1080500
9600
27558
19730
821777
584777
250
SC
0
O
C
C
C
0
C
O
C
0
C
E
E
TOTAL
EMISSIONS
310000
25500
175793
1500
58750
255
1085700
9600
27808
21922
853020
589772
250
D-9
-------
Emissions of Methylene chloride (CAS 000075092) 3
13:44 Tuesday, May 5, 1992
- SIC-283 -
(continued)
SIC THIS ID
283 10901CBGGYOLOMI
283 27835BRRGHINTER
283 07083SCHRN1011M
283 00617PFZRPHIGHW
283 80301HSRCH4750N
283 27597GLXNC1011N
283 94303LZCRP2575H
283 45215MRRLL2110E
283 80301SYNTX2075N
283 19382WYTHY611EN
283 07463BCRFT12IND
283 08902RSQBBONESQ
283 47721BRSTL2404P
FACILITY NAME
CIBA-GEIGY CORP. PHARMACEUTICALS DIV.
BURROUGHS WELLCOME CO.
SCHERING CORP.
PFIZER PHARMACEUTICALS INC.
HAUSER CHEMICAL RESEARCH INC.
GLAXO INC. TECHNICAL OPERATIONS DIV.
ALZA CORP.
MERRELL DOW PHARMACEUTICALS INC.
SYNTEX CHEMICALS INC.
WYETH-AYERST LABORATORIES INC.
BIOCRAFT LABORATORIES INC.
E.R. SQUIBB & SONS
MEAD JOHNSON & CO. EVANSVILLE PLANT
LOCATION
SUFFERN, NY
GREENVILLE, NC
UNION, NJ
BARCELONETA, PR
BOULDER, CO
ZEBULON, NC
PALO ALTO, CA
CINCINNATI, OH
BOULDER, CO
WEST CHESTER, PA
WALDWICK, NJ
NORTH BRUNSWICK, NJ
EVANSVILLE, IN
ONSITE
03
04
04
05
04
04
04
04
05
05
04
04
04
FUGITIVE
EMISSIONS
2974
13000
0
24000
61400
2290
250
400
250
4800
2514
4100
250
FC
0
c
o
o
CM
O
O
O
0
O
O
O
o
PARENT COMPANY
CIBA-GEIGY CORP. USA
WELLCOME FOUNDATION LTD.
SCHERING-PLOUGH CORP.
PFIZER INC.
NA
GLAXO ENTERPRISES INC.
NA
MARION MERRELL DOW INC.
SYNTEX (USA) INC.
AMERICAN HOME PRODUCTS
BIOCRAFT LABORATORIES INC.
BRISTOL-MYERS SQUIBB CO.
BRISTOL-MYERS SQUIBB CO.
STACK
EMISSIONS
14978
433000
76263
37100
0
155334
3434
25000
61300
28400
6694
4100
51300
SC
C
C
O
0
C
0
C
O
O
O
0
C
TOTAL
EMISSIONS
17952
446000
76263
61100
61400
157624
3684
25400
61550
33200
9208
8200
51550
D-10
-------
Emissions of Methylene Chloride (CAS 000075092) 4
13:44 Tuesday, May 5, 1992
- SIC=283 -
(continued)
SIC THIS ID
283 00617BBTTCROADN
283 49424PRKDV188HO
283 07901CBGGY556MO
283 13221BRSTLTHOMP
283 10965LDRLLNORTH
283 60064BBTTL1400N
283 00701RCHPRSTATE
283 21225KNSCL6118R
283 56623RDRWL210MA
283 19801NRMCF500OL
283 00671KYPHRPRIDC
283 00661SQBBMSTATE
283 07072RSYNCFOOTO
FACILITY NAME
ABBOTT CHEMICALS INC.
PARKE-DAVIS DIV. OF WARNER-LAMBERT CO.
CIBA-GEIGY CORP. PHARMACEUTICALS OIV.
BRISTOL-MYERS SQUIBB CO. INDUSTRIAL DIV.
LEDERLE LABORATORIES
ABBOTT LABORATORIES
ROCHE PRODUCTS INC.
KANASCO LTD.
REID-ROWELL INC.
NORAMCO OF DELAWARE INC.
SCHERING-PLOUGH PRODUCTS INC. KEY PHARMA
SQUIBB MFG. INC.
ARSYNCO INC.
LOCATION
BARCELONETA, PR
HOLLAND, MI
SUMMIT, NJ
SYRACUSE, NY
PEARL RIVER, NY
NORTH CHICAGO, IL
MANATI, PR
BALTIMORE, MD
BAUDETTE, MN
WILMINGTON, DE
LAS PIEDRAS, PR
HUMACAO, PR
CARLSTADT, NJ
ONSITE
05
04
05
05
04
05
04
05
04
05
05
05
04
FUGITIVE
EMISSIONS
784762
1100
0
190000
0
7700
4914
1500
0
11362
41000
95640
108778
FC
C
0
C
C
0
o
o
0
E
E
0
0
PARENT COMPANY
ABBOTT LABORATORIES INC.
WARNER LAMBERT CO.
CIBA-GEIGY CORP.
BRISTOL-MYERS SQUIBB CO.
AMERICAN CYANAMID CO.
ABBOTT LABORATORIES INC.
HOFFMANN-LA ROCHE LTD.
SOLVAY PHARMACEUTICAL INC.
JOHNSON & JOHNSON
SCHERING CORP.
BRISTOL-MYERS SQUIBB CO.
ACETO CHEMICAL CO.
STACK
EMISSIONS
1741170
5
13400
110000
3300
117550
13608
1400
100117
19815
54800
93260
16821
SC
C
0
C
E
0
O
0
0
C
E
O
O
0
TOTAL
EMISSIONS
2525932
1105
13400
300000
3300
125250
18522
2900
100117
31177
95800
188900
125599
D-ll
-------
Emissions of Methylene Chloride (CAS 000075092) 5
13:44 Tuesday, Nay 5, 1992
- SIC-283 -
(continued)
SIC TRIS ID
283 08807MRCNCEASTM
283 11590TSHCN125ST
283 91324MRKR 19901
283 47905LLLLYLILLY
283 19428SMTHK900RI
283 60077GDSRL4901S
283 00628LLLLY65THI
283 08807MRCNCEASTM
283 07110HFFMN340KI
283 49001THPJH7171P
283 46285LLLLYLILLY
283 46285LLLLY1555K
283 47842LLLLYSTATE
FACILITY NAME
AMERICAN CYANAMID CO. LEDERLE LABORATORI
TISHCON CORP.
3M RIKER
ELI LILLY & CO. TIPPECANOE LABORATORIES
SMITHKLINE BEECHAM PHARMACEUTI CALS
G. D. SEARLE & CO.
ELI LILLY INDUSTRIES INC.
AMERICAN CYANAMID CO. LEDERLE LABORATORI
HOFFMANN-LA ROCHE INC.
UPJOHN CO. PRODUCTION FACILITY
ELI LILLY & CO. LILLY CORPORATE CENTER
ELI LILLY & CO. LILLY INDUSTRIAL CENTER
ELI LILLY & CO. CLINTON LABORATORIES
LOCATION
BRIDGEWATER, NJ
WESTBURY, NY
NORTHRIDGE, CA
SHADELAND, IN
CONSHOHOCKEN, PA
SKOKIE, IL
CAROLINA, PR
BRIDGEWATER, NJ
NUTLEY, NJ
PORTAGE, MI
INDIANAPOLIS, IN
INDIANAPOLIS, IN
CLINTON, IN
ONSITE
04
03
03
06
04
04
03
04
05
06
03
04
06
FUGITIVE
EMISSIONS
343
0
1560
180000
250
3200
18000
597
12369
662600
'6500
11000
1600000
FC
0
C
O
E
0
0
O
0
E
C
O
C
PARENT COMPANY
AMERICAN CYANAMID CO.
TISHCON CORP.
3M CO.
ELI LILLY &. CO.
SMITHKLINE BEECHAM PHARMACEUTI
MONSANTO CO.
ELI LILLY &. CO.
AMERICAN CYANAMID CO.
ROCHE HOLDINGS INC.
UPJOHN CO.
ELI LILLY & CO.
ELI LILLY & CO.
ELI LILLY & CO.
TOTAL
EMISSIONS
27688
190971
17160
710000
1950
4400
35000
29502
18741
2964900
7700
211000
2410000
STACK
EMISSIONS
27345
190971
15600
530000
1700
1200
17000
28905
6372
2302300
1200
200000
810000
SC
0
C
C
O
0
O
C
O
0
0
C
O
0
D-12
-------
Emissions of Methylene Chloride (CAS 000075092) 6
13:44 Tuesday, May 5, 1992
- SIC=283 -
(continued)
SIC
283
283
283
283
283
283
283
283
SIC
TRIS ID
95688LZCRP700EU
19130SMTHK1500S
08854BCHML101PO
92121MLTPL3550G
92713NBLCN17802
63141KVFHR2303S
00732BLCHMRDNO1
08876HCHSTRTE20
FACILITY NAME
ALZA CORP.
SMITHKLINE BEECHAM PHARMACEUTICALS
SMITHKLINE BEECHAM PHARMACEUTICALS
MULTIPLE PEPTIDE SYSTEMS L.P.
ANABOLIC INC.
KV PHARMACEUTICAL CO.
BILCHEM LTD.
HOECHST CELANESE CORP. LIFE SCIENCES
LOCATION
VACAVILLE, CA
PHILADELPHIA, PA
PISCATAWAY, NJ
SAN DIEGO, CA
IRVINE, CA
SAINT LOUIS, MO
PONCE, PR
SOMERVILLE, NJ
PARENT COMPANY
NA
SMITHKLINE BEECHAM CORP.
SMITHKLINE BEECHMAN CORP.
NA
NA
NA
BOHERINGER INGELHEIM INC.
HOECHST CELANESE CORP.
ONSITE
05
04
05
03
04
04
04
03
FUGITIVE
EMISSIONS
3563
5
750
750
250
0
1410
250
4385303
FC
0
0
O
O
0
O
C
STACK
EMISSIONS
24693
55000
5100
0
14900
299733
27229
0
12545380
SC
0
C
E
M
C
O
NA
TOTAL
EMISSIONS
28256
55005
5850
750
15150
299733
28639
250
16930683
D-13
-------
Key:
SIC =
TRIS =
CAS =
WC
particulates;
WTC =
following.
Standard Industrial Classification
Toxic Chemical Release Inventory System
Chemical Abstract Service Registry Number
General Wastestream type; where
A = Gaseous (gases, vapors, airborne
W = Wastewater (aqueous waste),
L = Liquid Waste (non-aqueous waste), and
S = Solid Waste (including sludges and slurries).
Waste Treatment Code; as indicated by the
Air Emissions Treatment
A01 Flare
A02 Condenser
A03 Scrubber
A04 Absorber
A05 Electrostatic Precipitator
A06 Mechanical Separation
A07 Other Air Emission Treatment
Biological Treatment
Bll Biological Treatment -
B21 Biological Treatment -
B31 Biological Treatment -
B99 Biological Treatment -
Chemical Treatment
- Aerobic
- Anaerobic
- Facultative
- Other
C01 Chemical Precipitation -- Lime or Sodium Hydroxide
C02 Chemical Precipitation -- Sulfide
C09 Chemical Precipitation -- Other
Cll Neutralization
C21 Chromium Reduction
C31 Complexed Metals Treatment (other than pH Adjustment)
C41 Cyanide Oxidation -- Alkaline Chlorination
C42 Cyanide Oxidation -- Electrochemical
C43 Cyanide Oxidation -- Other
C44 General Oxidation (including Disinfection) --
Chlorination
C45 General Oxidation (including Disinfection) -- Ozonation
C46 General Oxidation (including Disinfection) -- Other
C99 Other Chemical Treatment
D-14
-------
Recovery/Reuse
R01
R02
R03
R04
R09
Rll
R12
R13
R14
R19
R21
R22
R23
R24
R26
R29
R99
Reuse as Fuel --
Reuse as Fuel --
Industrial Kiln
Industrial Furnace
Reuse as Fuel -- Boiler
Reuse as Fuel -- Fuel Blending
Reuse as Fuel -- Other
Solvents/Organics Recovery -
Solvents/Organics Recovery -
Solvents/Organics Recovery -
Solvents/Organics Recovery -
Solvents/Organics Recovery -
Metals Recovery -- Electrolytic
Metals Recovery -- Ion Exchange
Metals Recovery -- Acid Leaching
Metals Recovery -- Reverse Osmosis
Metals Recovery -- Solvent Extraction
Metals Recovery -- Other
Other Reuse or Recovery
Batch Still Distillation
Thin-Film Evaporation
Fractionation
Solvent Extraction
Other
Solidification/Stabilization
G01 Cement Processes (including Silicates)
G09 Other Pozzolonic Processes (including Silicates)
Gil Asphaltic Processes
G21 Thermoplastic Techniques
G99 Other Solidification Processes
Incineration/Thermal Treatment
F01 Liquid Injection
Fll Rotary Kiln with Liquid Injection Unit
F19 Other Rotary Kiln
F31 Two Stage
F41 Fixed Hearth
F42 Multiple Hearth
F51 Fluidized Bed
F61 Infra-Red
F71 Fume/Vapor
F81 Pyrolytic Destructor
F82 Wet Air Oxidation
F83 Thermal Drying/Dewatering
F99 Other Incineration/Thermal Treatment
D-15
-------
Physical Treatment
P01 Equalization
P09 Other Blending
Pll Settling/Clarification
P12 Filtration
P13 Sludge Dewatering (non-thermal)
P14 Air Flotation
P15 Oil Skimming
P16 Emulsion Breaking -- Thermal
P17 Emulsion Breaking -- Chemical
P18 Emulsion Breaking -- Other
P19 Other Liquid Phase Separation
P21 Adsorption -- Carbon
P22 Adsorption -- Ion Exchange (other than for
recovery/reuse)
P23 Adsorption -- Resin
P29 Adsorption -- Other
P31 Reverse Osmosis (other than for recovery/reuse)
P41 Stripping -- Air
P42 Stripping -- Steam
P49 Stripping -- Other
P51 Acid Leaching (other than for recovery/reuse)
P61 Solvent Extraction (other than for recovery/reuse)
P99 Other Physical Treatment
1C = Influent Concentration; where
1 = Greater than 1%,
2 = 100 parts per million (ppm; 0.01%) to 1% (10,000 ppm)
3=1 ppm to 100 ppm,
4=1 part per billion (ppb) to 1 ppm, and
5 = Less than 1 ppb.
STI = Sequential Treatment; where
Y indicates that individual treatment steps are used in a
series to treat the toxic chemical and there is no data
on the efficiency of each step, however, an estimate of
overall efficiency of the treatment sequence can be
estimated.
EFFIC = Efficiency Estimate (i.e., refers to the percent
destruction, degradation, conversion, or removal of the
listed toxic chemical from the waste stream.
OD = Operating Data; where
Y = The treatment efficiency estimate is based on actual
operating data,
N = The treatment efficiency is not based on actual
operating data, and
NA = Not applicable.
D-16
-------
Parent Company = the highest level company, located in the
Unites States, that directly owns at least
50% of the voting stock.
On-Site = The maximum quantity of the chemical (e.g., in
storage tanks, process vessels, on-site shipping
containers) at your facility at any time during
the calendar year. The following codes represent
the weight range in pounds on-site.
WEIGHT RANGE IN POUNDS
Range Code From. . . To ...
01
02
03
04
05
06
07
08
09
10
11
1
10
50
100
500
1
1,
10,
100,
,000,
,000,
,000,
,000,
,000,
0
100
000
000
000
000
000
000
000
000
billion
9
49
99
499
999
9,
99,
999,
,999,
,999,
,999,
,999,
,999,
more than
billion
99
999
999
999
999
999
999
999
999
999
1
Fugitive Emissions = all releases to the air that are not
released through stacks, vents, ducts, pipes, or any other
confined air stream (pounds/year).
FC = Basis of Fugitive Emissions Estimate.
SC = Basis of Stack Emissions Estimate.
FC and SC codes are as follows:
M - Estimate is based on monitoring data or measurements
for the toxic chemical as released to the environment
and/or off-site facility.
C - Estimate is based on mass balance calculations, such
as calculation of the amount of the toxic chemical in
streams entering and leaving process equipment.
E - Estimate is based on published emission factors, such
as those relating release quantity to through-put or
equipment type (e.g., air emission factors).
D-17
-------
0 - Estimate is based on other approaches such as
engineering calculations (e.g., estimating
volatilization using published mathematical formulas)
or best engineering judgement. This would include
applying an estimated removal efficiency to a waste
stream, even if the composition of the stream before
treatment was fully identified through monitoring
data.
Source: Toxic Chemical Release Inventory Reporting Form R and
Instructions, Revised 1990 Version, Section 313 of the
Emergency Planning and Community Right-to-Know Act
(Title III of the Superfund Amendments and
Reauthorization Act of 1986) . U.S. Environmental
Protection Agency, Office of Toxic Substances,
Washington, DC, EPA 560/4-91-007, January 1991.
D-18
-------
APPENDIX E
CALCULATION OF
UNCONTROLLED OPEN-TOP VAPOR CLEANER EMISSION FACTOR
INCORPORATING RECYCLE
E-l
-------
EXAMPLE CALCULATION: UNCONTROLLED EMISSION FACTOR CONSIDERING RECYCLE
• A material balance is used to estimate emission factors
(kg emitted/kg fresh solvent used) considering off-site
waste solvent recycle. OTVC factors are shown as an
example.
• The emission factor for OTVC not considering waste solvent
recycle is 0.66 kg emitted/kg used. The remainder of usage
(.34 kg/kg) becomes waste solvent.
• Let x - recycled solvent use.
• For every 1 kg of fresh (virgin) solvent used:
Total solvent use = 1 + x
Total air emissions = 0.66 (solvent use) =0.66 (1 +
x)
Waste solvent =0.34 (1 + x)
0.66 (1 + x) air emissions
t
solvent use
1 kg + x kg
OTVC
0.34 (1 + x) waste solvent
It is assumed that 75% of waste solvent is recovered by off-
site solvent recyclers and returned for use in cleaning.
The other 25% is unrecovered and is disposed of.
0.66 (1 + x) air emissions
t
solvent use
1 kg + x kg
0.75 [0.34 (1 + x)]
recycled solvent <-
OTVC
0.34 (1 + x)
— waste solvent
0.25 [0.34 (1 + x)]
—> unrecovered
solvent to
disposal
E-2
-------
• Calculate amount of recycled solvent used
x = 0.75 [0.34(1 + x)]
x = 0.342
(kg of recycled solvent used per kg fresh solvent
used)
• Calculate air emissions
x = 0.66 (1 + x) =0.89
(kg emitted to the air per kg fresh solvent)
• Thus, emission factor for OTVC considering recycle =
0.89 kg/kg fresh solvent use.
Source: Memorandum from R. C. Mead and R. F. Pandullo, Radian
Corporation, to D. Beck, U.S. Environmental Protection
Agency. Calculation of Number of Organic Solvent Cleaners
and Solvent Emissions and Use Per Model Plant. September 8,
1987.
E-3
------- |