Environmental Protection
Aowwy
AIR
Offia* of Air Quality
Planning And Standard*
RMMroh Triangle Park, NC 27711
EPA-454/R-96-008
November 1996
LOCATING AND ESTIMATING
AIR EMISSIONS FROM
SOURCES OF 1,3-BUTADIENE
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EPA 454/R-96-008
LOCATING AND ESTIMATING AIR EMISSIONS
FROM SOURCES OF 1,3-BUTADIENE
Office Of Air Quality Planning And Standards
Office Of Air And Radiation
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
November 1996
\. Environmental Protection Agency
jion 5, library (PL-12J)
77 West Jackson Boufevard, 12th Floor
Chicago, IL 60604-3590
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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. Mention of trade names
and commercial products does not constitute endorsement or recommendation for use.
EPA-454/R-96-008
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EXECUTIVE SUMMARY
The 1990 Clean Air Act Amendments contain a list of 189 hazardous air pollutants
(HAPs) which the U.S. Environmental Protection Agency must study, identify sources of, and
determine if regulations are warranted. One of these HAPs, 1,3-butadiene (butadiene), is the
subject of this document. This document describes the properties of butadiene as an air
pollutant, defines its production and use patterns, identifies source categories of air emissions,
and provides butadiene emissions data in terms of emission factors and national inventory
estimates. The document is a part of an ongoing EPA series designed to assist the general public
at large, but primarily State/local air agencies, in identifying sources of HAPs and determining
emissions estimates.
Butadiene is primarily used in the manufacture of synthetic elastomers (rubbers, latexes)
and for producing raw materials for nylon. Butadiene is emitted into the atmosphere from its
production, its use as a chemical feedstock in the production of other chemicals, the use of these
other chemicals, mobile sources, and from a wide variety of miscellaneous processes involving
fossil fuel and biomass combustion, petroleum refining, secondary lead smelting, and
wastewater treatment.
Including only sources for which estimates are available or can be calculated, total
nationwide emissions are estimated at 121,002 tons per year (109,775 Mg/yr). The primary
sources of butadiene emissions on a national level are on-road mobile (47%) and off-road
mobile (35%). Table ES-1 illustrates the national emissions estimates developed for the more
predominant butadiene categories. The main butadiene air emissions sources are on-road
mobile, off-road mobile, biomass burning, butadiene users, and petroleum refining. Some of
these estimates for the non-fuel combustion sources were obtained from the reports required
under the Superfund Amendment and Reauthorization Act (SARA), Title III, Section 313.
Other estimates are a function of national activity data combined with the best available
emission factors.
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Table ES-1. National Emission Estimates by Source Category*
Mobile
Stationary
Total
Source
On-road
Off-road
General aviation and air taxis
Biomass burning
(forest fires & prescribed burning)
Major butadiene usersb
Petroleum refining
Butadiene production
Secondary lead smelting
Miscellaneous other sources0
Applicable
Year
1992
1990
1994
1989
1992
1992
1992
1990
1992
Tons (Mg)
56,786(51,517)
41,883 (37,996)
107 (97)
19,931(18,082)
1,405 (1,275)
219(199)
191 (173)
134 (122)
106 (96)
121,049(109,004)
Percent
47.3
34.9
0.1
16.0
1.2
0.2
0.2
0.1
0.1
100.1
1 Only sources for which estimates were available or could be calculated are included. For example, emissions from
open burning of tires have not been included.
b Includes following SIC Codes:
28 Chemicals and allied products
2812 Alkalies and chlorine
2819 Industrial inorganic chemicals, nee
2821 Plastics materials synthetic resins and nonvulcanizable elastomers
2822 Synthetic rubber (vulcanizable elastomers)
2865 Cyclic organic crudes and intermediates, and organic dyes and pigments
2869 Industrial organic chemicals, nee
2879 Pesticides and agricultural chemicals, nee
2891 Adhesives and sealants
2899 Chemicals and chemical preparations, nee
c Other sources reporting under SARA 313 include facilities identified with the following SIC Codes. Also included
are two facilities without SIC Codes but which account for 15 tons per year (14 Mg/yr) combined, and one facility
with an SIC Code that is not listed but which reported 0.04 tons per year (0.04 Mg/yr).
2046 Wet com milling
2369 Girl's, children's, and infant's outwear, nee
2621 Paper mills
3312 Steel works, blast furnaces (including coke ovens), and rolling mills
3579 Office machines, nee
8731 Commercial physical and biological research
IV
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TABLE OF CONTENTS
Section Page
EXECUTIVE SUMMARY iii
LIST OF TABLES viii
LIST OF FIGURES xii
1.0 PURPOSE OF DOCUMENT 1-1
2.0 OVERVIEW OF DOCUMENT CONTENTS 2-1
3.0 BACKGROUND 3-1
3.1 NATURE OF THE POLLUTANT 3-1
3.2 OVERVIEW OF PRODUCTION AND USE 3-3
3.3 OVERVIEW OFEMISSIONS 3-5
4.0 EMISSIONS FROM BUTADIENE PRODUCTION 4-1
4.1 BUTADIENE PRODUCTION 4-2
4.1.1 Process Descriptions 4-2
4.1.2 Emissions 4-11
5.0 EMISSIONS FROM MAJOR USES OFBUTADffiNE 5-1
5.1 STYRENE-BUTADIENE COPOLYMER PRODUCTION 5-2
5.1.1 Process Description 5-3
5.1.2 Emissions 5-5
5.2 POLYBUTADffiNE PRODUCTION 5-10
5.2.1 Process Description 5-10
5.2.2 Emissions 5-11
5.3 ADIPONITRILE PRODUCTION 5-16
5.3.1 Process Description 5-16
5.3.2 Emissions 5-16
5.4 NEOPRENE PRODUCTION 5-20
5.4.1 Process Description 5-21
5.4.2 Emissions 5-23
5.5 ACRYLONITRILE-BUTADIENE-STYRENE COPOLYMER
PRODUCTION 5-26
5.5.1 Process Description 5-27
5.5.2 Emissions 5-34
5.6 NITRILE ELASTOMER PRODUCTION 5-36
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TABLE OF CONTENTS, continued
Section Page
5.6.1 Process Description 5-37
5.6.2 Emissions 5-40
6.0 BUTADIENE EMISSIONS FROMMOBILE SOURCES 6-1
6.1 ON-ROAD MOBILE SOURCES 6-1
6.2 OFF-ROAD MOBILE SOURCES 6-4
6.2.1 Marine Vessels 6-9
6.2.2 Locomotives 6-11
6.2.3 Aircraft 6-12
6.2.4 Rocket Engines 6-15
7.0 EMISSIONS FROM MISCELLANEOUS SOURCES OF BUTADIENE 7-1
7.1 MISCELLANEOUS USES OF BUTADIENE IN CHEMICAL
PRODUCTION 7-1
7.1.1 Product and Process Descriptions 7-2
7.1.2 Emissions 7-10
7.2 INDIRECT SOURCES OF BUTADIENE 7-13
7.2.1 Vinyl Chloride Monomer and Polyvinyl Chloride Production 7-13
7.2.2 Publicly Owned Treatment Works 7-14
7.2.3 Secondary Lead Smelting 7-14
7.2.4 Petroleum Refining 7-15
7.2.5 Combustion Sources 7-16
7.3 OTHER BUTADIENE SOURCES 7-22
8.0 SOURCE TEST PROCEDURES 8-1
8.1 EPA REFERENCE METHOD 18 8-1
8.2 NIOSH METHOD 1024 8-4
8.3 FEDERAL TEST PROCEDURE 8-5
8.4 AUTO/OIL AIR QUALITY IMPROVEMENT RESEARCH PROGRAM
SPECIATION METHOD 8-7
9.0 REFERENCES 9-1
APPENDICES
Appendix A - Emission Factor Summary Table A-l
Appendix B - Estimating Methods for National Butadiene Emission Sources B-l
References for Appendix B B-15
VI
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TABLE OF CONTENTS, continued
Appendix C - Facility-Specific Emissions Data from EPA Section 114
Responses C-l
References for Appendix C C-30
Appendix D - Estimation Methods for Equipment Leaks D-l
References for Appendix D D-7
Appendix E - Summary of 1992 TRI Air Emissions Data for 1,3-Butadiene E-l
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LIST OF TABLES
Table Page
ES-1 National Emission Estimates by Source Category iv
3-1 Physical and Chemical Properties of 1,3-Butadiene 3-2
4-1 Butadiene Production Facilities 4-3
4-2 Butadiene Yields from Recovery Using a Mixed-C4 Stream Produced from
Various Feedstocks 4-4
4-3 Typical Composition of Mixed-C4 Stream Formed from Naphtha Feedstock Used
to Produce Ethylene 4-6
4-4 Typical Composition of n-Butenes Oxidative Dehydrogenation Reactor Product
Stream 4-10
4-5 Summary of Emission Factors for Butadiene Production Facilities 4-14
4-6 VOC Emissions Reduction Efficiencies of Control Devices Used to Estimate
Current Butadiene Emissions 4-15
4-7 Average Butadiene Emission Rates for Process Equipment Component Leaks .... 4-17
4-8 Variability in Facility-Specific Emission Rates for Equipment Leaks 4-18
4-9 Control Techniques and Efficiencies Applicable to Equipment Leak Emissions ... 4-19
5-1 Typical Recipe for Emulsion SBR 5-5
5-2 Styrene-Butadiene Elastomer and Latex Production Facilities 5-6
5-3 Summary of Emission Factors for SB Copolymer Production Facilities 5-8
5-4 Polybutadiene Production Facilities 5-11
5-5 Summary of Emission Factors for Polybutadiene Production Facilities 5-14
5-6 Adiponitrile Production Facilities 5-17
5-7 Summary of Emission Factors for Adiponitrile Production Facilities 5-19
5-8 Chloroprene/Neoprene Production Facilities 5-21
5-9 Summary of Emission Factors for Neoprene Production Facilities 5-25
viii
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LIST OF TABLES, continued
Table Page
5-10 Short-Term Emissions from Neoprene Production Facilities 5-27
5-11 Acrylonitrile-Butadiene-Styrene Resin Production Facilities 5-28
5-12 Summary of Emission Factors for ABS Production Facilities, Emulsion Process . . . 5-35
5-13 Nitrile Elastomer Production Facilities 5-37
5-14 Summary of Emission Factors for Nitrile Elastomer Production Facilities 5-41
6-1 Butadiene Emission Factors for 1990 Taking into Consideration Vehicle Aging .... 6-3
6-2 Off-Road Equipment Types and Butadiene Emission Factors Included in the
NEVES 6-5
6-3 Butadiene Emission Factors for Commercial Marine Vessels 6-10
6-4 Butadiene Emission Factors for Locomotives 6-12
6-5 Butadiene Content in Aircraft Landing and Takeoff Emissions 6-13
6-6 Butadiene Emission Factors for General Aviation and Air Taxis 6-15
7-1 Miscellaneous Uses of Butadiene in Chemical Production 7-3
7-2 Summary of Emission Factors and Annual Emissions from Equipment Leaks for
Miscellaneous Chemicals Production Facilities 7-11
7-3 Emission Factors for 1,3-Butadiene for Burning of Yard Waste, Land
Clearing/Burning, and Slash Burning 7-19
7-4 Emission Factors for 1,3-Butadiene for Forest Fires and Prescribed Burning by
Fuel Type 7-20
7-5 Emission Factors for 1,3-Butadiene from Open Burning of Tires 7-21
7-6 Potential Source Categories of Butadiene Emissions 7-23
IX
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LIST OF TABLES, continued
Table Page
A-l Summary of Emission Factors by Source Classification Code A-l
B-l 1992 On-Road Butadiene Emissions B-2
C-l Butadiene Production Facilities for which 1984 Emissions Data are Available C-2
C-2 Butadiene Emissions (1984) from Process Vents at Olefins and Butadiene
Production Facilities C-3
C-3 Summary of Butadiene Emissions (1987) from Equipment Leaks at Nine
Production Facilities C-4
C-4 Butadiene Emissions (1984) from Secondary Sources at Butadiene Production
Facilities Using the Recovery from a Mixed-C4 Stream Process C-5
C-5 Styrene-Butadiene Elastomer and Latex Production Facilities for which 1984
Emissions Data are Available C-6
C-6 Butadiene Emissions (1984) from Process Vents at SB Copolymer Production
Facilities C-7
C-7 Butadiene Emissions (1984) from Equipment Leaks at SB Copolymer Production
Facilities C-10
C-8 Butadiene Emissions (1984) from Secondary Sources at SB Copolymer
Production Facilities (Mg/yr) C-l 1
C-9 Polybutadiene Production Facilities for which 1984 Emissions Data are Available
C-13
C-10 Butadiene Emissions (1984) from Process Vents at Polybutadiene Production
Facilities C-14
C-l 1 Butadiene Emissions (1984) from Equipment Leaks at Polybutadiene Production
Facilities C-15
C-12 Butadiene Emissions (1984) from Secondary Sources at Polybutadiene
Production Facility (Mg/yr) C-16
C-13 Adiponitrile Production Facilities for which 1984 Emissions Data are Available . . C-17
C-14 Butadiene Emissions (1984) from Process Vents at Adiponitrile Production
Facilities C-l8
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LIST OF TABLES, continued
Table Page
C-15 Butadiene Emissions (1984) from Equipment Leaks at Adiponitrile Production
Facilities C-19
C-16 Butadiene Emissions (1984) from Secondary Sources at Adiponitrile Production
Facilities C-20
C-17 Chloroprene/Neoprene Production Facilities for which 1984 Emissions Data are
Available C-21
C-18 Butadiene Emissions (1984) from Neoprene Production Facilities C-22
C-19 Acrylonitrile-Butadiene-Styrene Resin Production Facilities for which 1984
Emissions Data are Available C-23
C-20 Butadiene Emissions (1984) from ABS Production Facilities C-24
C-21 Nitrile Elastomer Production Facilities for which 1984 Emissions Data are
Available C-26
C-22 Butadiene Emissions (1984) from Nitrile Elastomer Production Facilities C-27
C-23 Miscellaneous Uses of Butadiene for which Emissions Data are Available C-29
C-24 Butadiene Emissions from Process Vents Associated with Miscellaneous Uses of
Butadiene C-30
C-25 Butadiene Emissions from Equipment Leaks Associated with Miscellaneous Uses
of Butadiene C-32
D-1 SOCMI Average Total Organic Compound Emission Factors for Equipment
Leaks D-3
D-2 Refinery Average Emission Factors D-4
D-3 SOCMI Screening Value Range Total Organic Compound Emission Factors for
Equipment Leak Emissions D-5
D-4 Refinery Screening Ranges Emission Factors D-6
E-l Summary of 1992 TRI Air Emissions Data for 1,3-Butadiene E-l
XI
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LIST OF FIGURES
Figure Page
3-1 Chemical Production and Use Tree for 1,3-Butadiene 3-4
3-2 Relative Contributions to National Butadiene Emissions by Mobile and Point
Source Categories 3-7
3-3 Relative Contributions to Stationary Butadiene Emissions by Point Source
Categories 3-8
4-1 Process Diagram for Production of a Mixed-C4 Stream Containing Butadiene 4-5
4-2 Process Diagram for Butadiene Production by Recovery from a Mixed-C4 Stream . . 4-7
4-3 Process Diagram for Production of Butadiene by the Oxidative Dehydrogenation
of Butene 4-9
5-1 Process Diagram for Production of SB Copolymer 5-4
5-2 Process Diagram for Production of Polybutadiene Rubber 5-12
5-3 Process Diagram for Production of Adiponitrile 5-18
5-4 Process Diagram for Production of Chioroprene Monomer 5-22
5-5 Flow Sheet for the Production of Neoprene 5-24
5-6 Process Diagram for Production of ABS/SAN via the Emulsion Process 5-29
5-7 Process Diagram for Production of ABS via the Suspension Process 5-32
5-8 Process Diagram for Production of Bulk ABS 5-33
5-9 Process Diagram for Production of Nitrile Elastomer 5-38
8-1 Integrated Bag Sampling Train 8-2
8-2 Vehicle Exhaust Gas Sampling System 8-6
XI1
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SECTION 1.0
PURPOSE OF DOCUMENT
The U.S. Environmental Protection Agency (EPA), 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, in turn, has led to attempts to
identify source/receptor relationships for these substances and to develop control programs to
regulate emissions. Unfortunately, limited information is available on the ambient air
concentrations of these substances or about 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 locating and estimating (L&E) documents such as
this one that compiles available information on sources and emissions of these substances. Other
documents in the series are listed below:
Substance
Acrylonitrile
Benzene (under revision)
Cadmium
Carbon Tetrachloride
Chlorobenzene (update)
Chloroform
Chromium (supplement)
Chromium
Coal and Oil Combustion Sources
EPA Publication Number
EPA-450/4-84-007a
EPA-450/4-84-007q
EPA-454/R-93-040
EPA-450/4-84-007b
EPA-454/R-93-044
EPA-450/4-84-007c
EPA-450/2-89-002
EPA-450/4-84-007g
EPA-450/2-89-001
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Substance
Cyanide Compounds
Epichlorohydrin
Ethylene Bichloride
Ethylene Oxide
Formaldehyde
Manganese
Medical Waste Incinerators
Mercury and Mercury Compounds
Methyl Chloroform
Methyl Ethyl Ketone
Methylene Chloride
Municipal Waste Combustors
Nickel
Perchloroethylene and
Trichl oroethy 1 ene
Phosgene
Polychlorinated Biphenyls (PCBs)
Polycyclic Organic Matter (POM)
(under revision)
Sewage Sludge Incinerators
Styrene
Toluene
Vinylidene Chloride
Xylenes
EPA Publication Number
EPA-454/R-93-041
EPA-450/4-84-007J
EPA-450/4-84-007d
EPA-450/4-84-0071
EPA-450/4-91-012
EPA-450/4-84-007h
EPA-454/R-93-053
EPA-453/R-93-023
EPA-454/R-93-045
EPA-454/R-93-046
EPA-454/R-93-006
EPA-450/2-89-006
EPA-450/4-84-007f
EPA-450/2-89-013
EPA-450/4-84-007i
EPA-450/4-84-007n
EPA-450/4-84-007p
EPA-450/2-90-009
EPA-454/R-93-011
EPA-454/R-93-047
EPA-450/4-84-007k
EPA-454/R-93-048
In addition, new documents currently under development will address lead, chlorinated
dibenzo-p-dioxins and chlorinated dibenzofurans, and arsenic and arsenic compounds.
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This document deals specifically with 1,3-butadiene, commonly referred to as
butadiene. Its intended audience includes Federal, State, and local air pollution personnel and
others who are interested in locating potential emitters of 1,3-butadiene and estimating their air
emissions.
Because of the limited availability of data on potential sources of 1,3-butadiene
emissions and the variability in process configurations, control equipment, and operating
procedure among facilities, this document is best used as a primer on (1) types of sources that
may emit 1,3-butadiene, (2) process variations and release points that may be expected, and
(3) available emissions information on the potential for 1,3-butadiene releases into the air. The
reader is cautioned against using the emissions information in this document to develop an exact
assessment of emissions from any particular facility. For facilities, most estimates are values
reported by the facilities in 1984 in response to EPA requests for information and therefore may
be out of date. Furthermore, not all facilities received requests, and those that received requests
did not always provide complete responses. For more accurate estimates, the reader should seek
more current and complete data.
It was thought at one point that the 1984 Chemical Manufacturers Association
(CMA) facility data could be updated using the Toxic Release Inventory (TRI). However,
because many of the chemical production facilities produce multiple chemicals, it was not
possible to accurately apportion the TRI data to the specific CMA facilities.
An effort was made to obtain more up-to-date information than the 1984 data. A
literature search was conducted and several databases were accessed. The most promising
sources of potential data are the current Polymers/Resins National Emission Standard for
Hazardous Air Pollutants (NESHAP) and Rubber Chemicals work. The polymers/resins
NESHAP was to have been completed and published by fall, 1994, but because of the
confidentiality of much of the data, it was not possible to obtain those data at the present time to
include in this L&E document. The process descriptions in this L&E document should not differ
greatly from those in the NESHAP. However, it is not certain at this time what data will be
available from the NESHAP and how the data might differ from what is presently in the L&E.
1-3
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The rubber chemicals work has been delayed, so that EPA can expand the
definition of "rubber chemicals" to include a broader category of chemicals. It is not expected
that information will be available in time to be included in this version of the Butadiene L&E.
It is possible, in some cases, that orders-of-magnitude differences may result
between actual and estimated emissions, depending on differences in source configurations,
control equipment, and operating practices. Thus, in all situations where an accurate assessment
of 1,3-butadiene emissions is necessary, the source-specific information should be obtained to
confirm the existence of particular emitting operations and the types and effectiveness of control
measures, and to determine the impact of operating practices. A source test and/or material
balance calculations should be considered as the best method of determining air emissions from
an operation.
Most of the emission factors for the basic production and intermediate product
sources presented in the text are based on the 1984 data. The supporting facility-specific data
are provided in Appendix C. The emission rates for equipment leaks were developed by the
CMA and are based on a 1989 study of equipment leak emissions at butadiene production
facilities. These CMA rates are significantly different from the Synthetic Organic Chemical
Manufacturing Industry (SOCMI) average emission rates,1 and, because they are specific to
butadiene, are assumed to better represent equipment leak emissions at other butadiene user
facilities; therefore, they were used to estimate annual emissions. Again, the reader should
collect facility-specific data for the most accurate estimates.
The chemical industry as a whole has done a lot to reduce emissions since the
early/mid 1980s as interest in air toxics has grown. A number of National Emission Standards
for Hazardous Air Pollutants (NESHAP) have been promulgated that are expected to reduce
butadiene emissions from facilities that are subject to the regulatory requirements. The recent
NESHAP that will impact butadiene emissions the most include the Hazardous Organic
NESHAP (HON) which has been promulgated April 22, 1994 and NESHAP for several of the
Polymers and Resins categories that are under development. Others include the NESHAP for
Publicly Owned Treatment Works, the Petroleum Refineries NESHAP and the NESHAP for
1-4
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secondary lead production. Specific requirements and impacts are not included in this
document. The reader should refer to the regulations to assess the reductions achieved.
The EPA also initiated a voluntary program in 1991 as a part of the Agency's
pollution prevention strategy. Known as the 33/50 Program, companies committed to reducing
facilities emissions for 17 high priority compounds. Although butadiene is not among the listed
compounds, reductions would be achieved where butadiene was co-located with a listed
compound or where shared equipment was modified to reduce emissions of the 17 high priority
compounds.
In addition to the information presented in this document, another potential
source of emissions data for 1,3-butadiene from facilities is the Toxic Chemical Release
Inventory (TRI) form required by Title m, Section 313 of the 1986 Superfund Amendments and
Reauthorization Act (SARA).2 Section 313 requires owners and operators of facilities in certain
Standard Industrial Classification Codes that manufacture, import, process, or otherwise use
toxic chemicals (as listed in Section 313) to report annually their releases of these chemicals to
all environmental media. As part of SARA 313, EPA provides public access to the annual
emissions data.
The TRI data include general facility information, chemical information, and
emissions data. Air emissions data are reported as total facility release estimates for fugitive
emissions and point source emissions. No individual process or stack data are provided to EPA
under the program. SARA Section 313 requires sources to use available stack monitoring data
for reporting but does not require facilities to perform stack monitoring or other types of
emissions measurement. If monitoring data are unavailable, emissions are to be quantified based
on best estimates of releases to the environment.
The reader is cautioned that TRI will not likely provide facility, emissions, and
chemical release data sufficient for conducting detailed exposure modeling and risk assessment.
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In many cases, the TRI data are based on annual estimates of emissions (i.e., on emission
factors, material balance calculations, and engineering judgment). We recommend the use of
TRI data in conjunction with the information provided in this document to locate potential
emitters of butadiene and to make preliminary estimates of air emissions from these facilities.
For mobile sources, more data are becoming available for on-road vehicles.
Additionally, the EPA model that generates emission factors undergoes regular update. The on-
road mobile sources section in this document should therefore be viewed as an example of how
emissions can be determined and the reader should look for more detailed data for the most
accurate estimates.
Limited data on off-road vehicles and other stationary sources are available.
However, with EPA's increased emphasis on air toxics, more butadiene data are likely to be
generated in the future.
As standard procedure, L&E documents are sent to government, industry, and
environmental groups wherever EPA is aware of expertise. These groups are given the
opportunity to review a document, comment, and provide additional data where applicable.
Where necessary, the document is then revised to incorporate these comments. Although this
document has undergone extensive review, there may still be shortcomings. Comments
subsequent to publication are welcome and will be addressed based on available time and
resources In addition, any information on process descriptions, operating parameters, control
measures, and emissions information that would enable EPA to improve on the contents of this
document is welcome. Comments and information may be sent to the following address:
Leader, Emission Factor and Methodologies Team
Emission Factor and Inventory Group (MD-14)
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
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SECTION 2.0
OVERVIEW OF DOCUMENT CONTENTS
This section briefly outlines the nature, extent, and format of the material
presented in the remaining sections of this report.
Section 3.0 provides a brief summary of the physical and chemical characteristics
of butadiene and an overview of its production, uses, and emissions sources. This background
section may be useful to someone who needs to develop a general perspective on the nature of
butadiene, how it is manufactured and consumed, and potential production, use, and mobile
sources of emissions.
Section 4.0 focuses on the production of butadiene and the associated air
emissions. For each major production source category described in Section 4.0, an example
process description and a flow diagram with potential emission points are given. Available
emissions estimates were used to calculate emission factor ranges that show the potential for
butadiene emissions before and after controls employed by industry. Also provided are
estimates of annual emissions from equipment leaks. Individual companies that are reported in
trade publications to produce butadiene are named.
Section 5.0 describes major source categories that use butadiene, primarily in the
manufacture of synthetic elastomers. For each major production process, a description(s) of the
process is given along with a process flow diagram(s). Potential emission points are identified
on the diagrams and emission ranges are presented as estimates are available. Ranges of annual
emissions due to equipment leaks are also given. Individual companies that use butadiene as a
feedstock are reported.
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Section 6.0 provides a brief summary on butadiene emissions from mobile
sources. The section addresses both on-road and off-road sources.
Section 7.0 summarizes the source categories—termed miscellaneous sources—that
use and potentially emit smaller quantities of butadiene. It also addresses emissions from
indirect sources such as treatment of butadiene-containing wastewater and other potential
sources that are not clearly users or indirect sources ("other" category). Limited information on
these sources is available; therefore, varying levels of detail on the processes, emissions, and
controls are presented. Locations of facilities for each source category as identified in the
literature are provided.
The final section, Section 8.0, summarizes available procedures for source
sampling and analysis of butadiene. This section provides an overview of applicable sampling
procedures and cites references for those interested in conducting source tests.
Appendix A presents a summary table of the emission factors contained in this
document. This table also presents the factor quality rating and the Source Classification Code
(SCC) or Area/Mobile Source (AMS) code associated with each emission factor.
Appendix B provides a brief description of the basis for the national emission
estimates appearing in Section 3.0. For each source, there is a description of the estimation
approach and an example calculation.
Appendix C provides facility-specific data taken from Section 114 responses
upon which the process vent and secondary source emission factors in Sections 4.0, 5.0, and 7.0
are based. Each facility has been assigned a letter code to prevent disclosure of its identity. In
general, the equipment leak emissions shown were calculated by applying average CMA
emission factors to the equipment component counts from the Section 114 responses. The
exceptions are butadiene producers and miscellaneous users. For producers, equipment counts
were summarized by CMA for 9 of the 11 facilities and the resulting emissions are presented as
the most recent data. For the miscellaneous users, estimates based on SOCMI factors were
2-2
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shown because equipment count data were not readily available to use with the average CMA
emission factors. These were calculated in earlier work done by EPA.
Appendix D presents the procedure for the derivation of butadiene equipment
leak emissions estimates associated with the production processes presented in Sections 4.0, 5.0,
and 7.0. Calculations for pump seals and pressure relief valves appear as examples of these
derivations.
Each emission factor listed in Sections 4.0 through 7.0 was assigned an emission
factor rating (A, B, C, D, E, or U) based on the criteria for assigning data quality ratings and
emission factor ratings as required in the document Technical Procedures for Developing AP-42
Emission Factors and Preparing AP-42 Sections3 The criteria for assigning the data quality
ratings to source tests are as follows:
A - Test(s) was performed by a sound methodology and reported in enough
detail for adequate validation. These tests are not necessarily EPA
reference test methods, although such reference methods are certainly to
be used as a guide.
B - Test(s) was performed by a generally sound methodology but lacked
enough detail for adequate validation.
C - Test(s) was based on a nonvalidated or draft methodology or lacked a
significant amount of background data.
D - Test(s) was based on a generally unacceptable method but may provide an
order-of-magnitude value for the source.
Once the data quality ratings for the source tests had been assigned, these ratings
along with the number of source tests available for a given emission point were evaluated.
Because of the almost impossible task of assigning a meaningful confidence limit to industry-
specific variables (e.g., sample size vs. sample population, industry and facility variability,
method of measurement), the use of a statistical confidence interval for establishing a
representative emission factor for each source category was not practical. Therefore, some
2-3
-------
subjective quality rating was necessary. The following factor quality ratings were used in the
emission factor tables in this document:
A - Excellent. The emission factor was developed only from A-rated test data
taken from many randomly chosen facilities in the industry population. The
source category is specific enough to minimize variability within the source
category population.
B - Above average. The emission factor was developed only from A-rated test
data from a reasonable number of facilities. Although no specific bias is evident,
it is not clear if the facilities tested represent a random sample of the industry. As
with the A rating, the source category is specific enough to minimize variability
within the source category population.
C - Average. The emission factor was developed only from A- and B-rated test
data from a reasonable number of facilities. Although no specific bias is evident,
it is not clear if the facilities tested represent a random sample of the industry. As
with the A rating, the source category is specific enough to minimize variability
within the source category population.
D - Below average. The emission factor was developed only from A- and B-rated
test data from a small number of facilities, and there may be reason to suspect that
these facilities do not represent a random sample of the industry. There also may
be evidence of variability within the source category population.
E - Poor. The emission factor was developed from C- and D-rated test data, and
there may be reason to suspect that the facilities tested do not represent a random
sample of the industry. There also may be evidence of variability within the
source category population.
U - Unrated or Unratable. The emission factor was developed from suspect data
with no supporting documentation to accurately apply an A through E rating. A
"U" rating may be applied in the following circumstances:4
Ul = Mass Balance (for example, estimating air emissions based
on raw material input, product recovery efficiency, and
percent control).
U2 = Source test deficiencies (such as inadequate quality
assurance/quality control, questionable source test methods,
only one source test).
U3 = Technology transfer.
U4 = Engineering judgement.
U5 = Lack of supporting documentation.
2-4
-------
This document does not contain any discussion of health or other environmental
effects of butadiene, nor does it include any discussion of ambient air levels.
2-5
-------
SECTION 3.0
BACKGROUND
3.1 NATURE OF THE POLLUTANT
Butadiene is a colorless, flammable gas with a pungent, aromatic odor. It has a
boiling point between 24.8 and 23 °F (-4 and -5°C). Table 3-1 summarizes butadiene's chemical
and physical properties.5'6 Although butadiene is insoluble in water, it is slightly soluble in
methanol and ethanol, and readily soluble at room temperature in common organic solvents such
as benzene and ether.7 It forms azeotropes with ammonia, methylamine, acetaldehyde, n-butene,
and 2-butene.5
Butadiene is a highly versatile raw material that is used commercially in a variety
of reactions. These include:
• Diels-Alder reactions with dienophiles to form a six-membered ring
compound with a 2,3 double bond,
« conversion to cyclic or open chain dimers and trimers,
• telomerization with active hydrogen compounds,
• addition reactions with electrophilic and free radical compounds,
• oxidation reactions,
• substitution reactions, and
• polymerization.
3-1
-------
TABLE 3-1. PHYSICAL AND CHEMICAL PROPERTIES OF 1,3-BUTADIENE
Property
Value
Structural Formula: CJH^ CHj.'CHCHiCHj
Synonyms: biethylene, bivinyl, butadiene, butadiene
monomer divinyl, erythrene, methylallene, pyrrolylene,
vinyl ethylene
CAS Registry Number: 106-99-0
Molecular Weight
Melting Point, °C
Boiling Point, °C
Partition Coefficient (log P, octanol/water)
Density at 20 °C, g/cm3
Vapor Density
Critical Density, g/cm3
Critical Temperature, °C
Critical Pressure, MPa (psi)
Critical Volume, mL/mol
Vapor Pressure, atm:
15.3°C
47.0°C
Flashpoint, °C
Heat of Vaporization, J/g (cal/g):
25 °C
bp
Heat of Fusion, J/g (cal/g)
Heat of Formation at.25°C, kJ/mol (kcal/mol):
Gas
Liquid
Free Energy of Formation at 25 °C, kJ/mol (kcal/mol)
Gas
Explosive Limits, vol % butadiene in air:
Lower
Upper
Solubility in Water at 20 °C, mg/L
54.09
-108.91
-4.41
1.99
0.6211
1.87
0.245
152
4.32 (626)
221
2.0
5.0
-105
389 (93)
418(100)
147.6 (35.28)
110.2(26.33)
88.7 (21.21)
150.7(36.01)
2.0
11.5
735
Source: References 5 and 6.
3-2
-------
Polymerization, with additions occurring at both the 1,2 and the 1,4 positions, are
the basis for synthetic elastomer production, the major use of butadiene.8
Because of its reactivity, butadiene is estimated to have an atmospheric lifetime
on the order of four hours, where atmospheric lifetime is defined as the time required for the
concentration to decay to 1/e (37 percent) of its original value.9 Actual lifetime depends on the
conditions at the time of release. The primary removal mechanisms are through chemical
reactions with hydroxyl radicals and ozone.9 Therefore, factors influencing butadiene's
atmospheric lifetime—time of day, sunlight intensity, temperature, etc.—also include those
affecting the availability of hydroxyl radicals and ozone.
3.2 OVERVIEW OF PRODUCTION AND USE
Butadiene production in the United States is accomplished through either of two
processes: recovery of butadiene from a mixed-C4 hydrocarbon stream generated during
ethylene production, or through oxidative dehydrogenation of n-butenes. Almost all,
[1 47 millions tons (1.33 million megagrams) in 1993] results from recovery of butadiene as a
byproduct of ethylene generation. Of the 10 U.S. producers, 8 are located in Texas and 2 in
Louisiana.8 The majority of these producers generate the feedstock at the same location as
butadiene production.8
Seventy-five percent of butadiene is used in synthetic elastomer production,
30 percent of which is dedicated to styrene-butadiene rubber; 20 percent to polybutadiene;
10 percent to styrene-butadiene latex; and 5 percent each to neoprene, acrylonitrile-butadiene-
styrene resin, and nitrile rubber. A second major use of butadiene is in adiponitrile production
(15 percent), the raw material for nylon 6,6 production. The remaining 10 percent is used for
miscellaneous products;8 exports comprise less than 1 percent.10 Figure 3-1 illustrates these uses
and the subsequent consumer end products.8'11'12'13'14'15'16
3-3
-------
Butadiene Production (80%)_
+ Imports (20%)
U)
.u
Styrene-Butidlene Rubbtr Production (SOS)
For/butadiene Production (20%)-
Adiponttrlk Production (15%)
' Styrene-Butadlene Latex Production (10%)
• Nooprene Rubb*r Production (5%) •
-Acrykmftrle-Butadlene-Styrene Resin Production (5%)~
• NRrk Rubber Production (5%p
Mlscelanoous (10%)
Tires and Tlr* Product* (60%)
Mechanical Rubber Ooodt (11%)
Automotive (8%)
Other (3%)
Automotive, Truck, But Tires (75%)
i High Impact Retkit (22%)
Industrial Product*, Other (3%)
Hexamethylenedlamlno (Nylon 6,6 Intermediate)
Carpet Backing (60%)
Piper Coatlnga (25%)
Pakita, Other (15%)
Mechanical (30%)
Industrial Rubber Oood* (30%)
> AdhesKres (12%)
Wire and Cable (6%)
Latexes (10%)
Consumer Products (6%)
Celular Rubber (4%)
Automotive (20%)
Applanees (18%)
Export! (17%)
Construction (16%)
Other (13%)
Electronics, Business Machines. Telecommunications (10%)
Custom Sheet (6%)
Hoses and Belting, Cable (25%)
Seals and Gaskets (15%)
Exports (15%)
Molded Ooods (13%)
Latex (13%)
Adheslves and Sealants (10%)
Sponges (4%)
Other (3%)
Footwear (2%)
a.
i
Figure 3-1. Chemical Production and Use Tree for 1,3-Butadiene
Source: Reference 7. 10, 11, 12, 13,14. 15
-------
Long-term growth in demand for butadiene is expected to be modest, with
reduced requirements for synthetic rubber because of quality and performance improvements in
automobile and other road tires. There will be some newer butadiene applications (sealants,
adhesives, processing aids for plastic industry) that will experience rapid growth in future years.
However, overall U.S. butadiene demand growth is not expected to exceed 2 percent per year,
and may well show a long term slow decline by 1995/1996.10
3.3 OVERVIEW OF EMISSIONS
Sources of butadiene emissions from its production and uses are typical of those
found at any chemical production facility:
• process vents,
• equipment leaks,
• waste streams (secondary sources),
• storage, and
• accidental or emergency releases.
Much of the available emissions data used to prepare this report were collected by EPA from
industry in 1984. Use of these estimates to represent sources at different locations is of limited
accuracy because of the differences in process configurations and plant operations. The
equipment leak emission factors are based on a 1989 CMA study. The CMA Butadiene Panel
collected monitoring data from nine of the facilities manufacturing butadiene to develop average
component-specific emission factors. Although the accuracy of applying these emission factors
to butadiene user facilities is undetermined, they are presented as an alternative to the SOCMI
emission factors previously developed by EPA.
Emissions data from several butadiene sources, including mobile, petroleum
refining, secondary lead smelting, tire burning, and biomass burning, have been added to this
update of the document and are described in Section 7.0.
3-5
-------
Estimated national emissions from on-road mobile sources amount to 56,786 tons
(51,517 Mg) based on butadiene emission factors developed by the EPA Office of Mobile
Sources17 and 1992 Department of Transportation data18 on vehicle miles travelled. For nonroad
mobile sources, the EPA Nonroad Engine Vehicle Emission Study (NEVES) provides an
average estimate of 41,883 tons (37,996 Mg). Three nonroad categories are not included in the
NEVES—locomotives, aircraft, and rockets. Of these, only estimates for general aviation and air
taxis have been developed. These account for 61 tons (55 Mg) and 46 tons (42 Mg),
respectively. For the other mobile sources, activity data were not readily available.
Estimates of national butadiene emissions from mobile and stationary sources are
shown in Figure 3-2, and Figure 3-3 shows a breakdown of stationary source emission estimates.
The estimates from butadiene production, major butadiene users, petroleum refining, and
miscellaneous "other" sources are based on SARA 313 Toxic Release Inventory data for 1992.
As mentioned above, the mobile estimates are based on EPA studies and Department of
Transportation data. The secondary lead smelting and biomass burning (forest fires and
prescribed burning) emission estimates are based on available emission factors combined with
activity data. Appendix B describes the basis for all of the national emission estimates.
Some butadiene sources discussed in this document did not have enough data to
estimate national emissions and are, therefore, not included in Figures 3-2 and 3-3. For
example, an emission factor for butadiene from open burning of tires was found in AP-42, but
the only available activity data were for tire incineration, not open burning.
3-6
-------
BMobil* >ourc*i, on-road (47.1%)
• Mobile tourcet, non-road (M.t%)
Oeioma** burning (16.0%)
DHiJor uterc of butadiene (1-2%)
• Petroleum refining (0.2%)
BButadlene production (0.2%)
•Mobile courcet, alrcraR (0.1%)
OSecondary lead smelting (0.1%)
• Mlkcallaneoua aoureea (0.1%)
Figure 3-2. Relative Contributions to National Butadiene Emissions by Mobile and Point
Source Categories
-------
U)
00
Bllomatt burning (»0.»%)
• Butadltna uaira (I.IOK)
Opatrotaum tanning (1.0IK)
QBuUdltn* produeOen (0.10%)
• secondary lead (O.ilS)
QMIacallantoua aourcai (O.(0%)
Figure 3-3. Relative Contributions to Stationary Butadiene Emissions by Point Source Categories
-------
SECTION 4.0
EMISSIONS FROM BUTADIENE PRODUCTION
This section discusses emissions from sources associated with butadiene
production. The information presented in this section includes identification of producers and
descriptions of typical production processes. Process flow diagrams are given, as appropriate,
with streams and vents labeled to correspond to the discussion in the text. Estimates of the
associated butadiene emissions are provided in the form of emission factors when data were
available to calculate them. Any known emission control practices are also discussed.
Much of the process vent and secondary source emissions data were taken from
facility-reported information based on responses to Section 114 requests in 1984.19 In many
cases, these responses were incomplete. Interested readers should therefore contact specific
facilities directly to determine the process in use, production volume, and control techniques in
place before applying any of the emission factors presented in this document. This document
will be reviewed for the need to provide newer data as they become available.
The equipment leak emission factors given in this section were calculated from
producer screening data collected by the Chemical Manufacturers' Association (CMA) in 1988.
This study is briefly described and the results presented both in terms of average component-
specific emissions factors and as annual emissions.
4-1
-------
4.1 BUTADIENE PRODUCTION
The 1,3-isomer of butadiene, the only commercially significant isomer, is a high-
x
volume intermediate organic chemical used to produce various types of rubber, resins, and
plastics. Butadiene is produced by two different processes in the United States. One process
involves the recovery of butadiene from a mixed-C4 hydrocarbon stream generated during
ethylene or other alkene production. The other process is the oxidative dehydrogenation of n-
butenes to produce butadiene.
The 10 facilities currently producing finished butadiene in the United States are
listed in Table 4-1.10 All of these facilities recover butadiene from a mixed-C4 stream. The
mixed-C4 streams feeding the recovery units are produced at olefins units co-located with the
recovery units at these facilities, with the exception of one facility that receives its feedstock
from an unidentified source. This facility also has the capacity to produce butadiene using the
oxidative dehydrogenation of n-butenes process. However, this capacity is being utilized to
dehydrogenate isobutane to isobutylene, for use in the manufacture of tert-butyl-methyl ether
(MTBE)10
4 1 1 Process Descriptions
Recovery of Butadiene from aMixed-C4 Stream
This process comprises two distinct steps. First, a mixed-C4 stream containing
butadiene is co-produced in an olefins plant during the cracking of large-molecule hydrocarbons
to manufacture ethylene or other alkenes. The mixed-C4 stream is then routed to a recovery unit,
where the butadiene is separated.
The amount of butadiene produced during ethylene manufacture is dependent on
both the type of hydrocarbon feedstock and the severity of the cracking operation. Typical
butadiene yields from ethylene production, based on various feedstocks, are summarized in
4-2
-------
TABLE 4-1. BUTADIENE PRODUCTION FACILITIES1
Company
Location
Capacity in 1993
tons/yr (Mg/yr)
Amoco Chemicals Company
Occidental Petrochemical
Exxon Chemicals Company
Lyondell Petrochemical Company
Shell Chemical Company
Texaco Chemical Company
Texas Petrochemicals Corporation1"
Chocolate Bayou, TX
Chocolate Bayou, TX
Corpus Christi, TX
Baton Rouge, LA
Baytown, TX
Channelview, TX
Deer Park, TX
Norco, LA
PortNeches, TX
Houston, TX
91,100(82,000)
67,800 (61,000)
111,100(100,000)
156,700(141,000)
121,100(109,000)
310,000(279,000)
126,700(114,000)
252,200 (227,000)
317,800(295,000)
403,300 (363,000)
Source Reference 10.
' The production process for all facilities is the recovery process. "Recovery" means butadiene as a
coproduct in ethylene production is recovered from the mixed-C4 stream.
h This facility is the only producer with on-purpose butylene dehydrogenation capacity, but this capacity is
being utilized to dehydrogenate isobutane to isobutylene, for use in the manufacture of MTBE. This
capacity is not included in the above totals. Effective January 1994. all of the Texas Petrochemicals
operations will be owned by Huntsman Chemical.
Table 4-2 l9 Heavier feedstocks (naphthas and gas oils) produce much larger quantities of
butadiene than do the lighter feedstocks.
A generalized block flow diagram of an olefins unit producing a mixed-C4 Co-
product stream, excluding the ethylene separation process, is shown in Figure 4-1.19 In olefins
production, a steam cracking furnace is used to crack the hydrocarbon feedstock (Step 1). The
heavy hydrocarbons are broken into two or more fragments, forming a stream of mixed
hydrocarbons. The concentration of butadiene in this mixed hydrocarbon stream varies with the
type of feedstock. The flue gas from the cracking furnace is vented to the atmosphere (Vent A).
4-3
-------
TABLE 4-2. BUTADIENE YIELDS FROM RECOVERY USING A MTXED-C4 STREAM
PRODUCED FROM VARIOUS FEEDSTOCKS'
Yield Ratio
Feedstock (butadiene/ethylene produced on a weight basis)
Ethane 0.01 - 0.02
Refinery offgas 0.05
Propane 0,05 - 0.085
n-Butane 0.07 - 0.085
Naphthas 0.13-0.18
Gas oils 0.176-0.247
Source: Reference 19.
* Refer to Figure 4-1 for a process diagram of mixed-C4 production olefms unit. Refer to Figure 4-2 for a diagram
of a butadiene recovery process.
After the cracking step, the mixed hydrocarbon stream is cooled (Step 2) and, if
naphtha or gas oils were the initial feedstock, the stream is sent to a gasoline fractionator
(Step 3). The fractionator is used to recover heavy hydrocarbons (C5 and higher). For some
olefms units, the quenching step shown occurs after gasoline fractionation. The mixed stream is
then compressed (Step 4) prior to removal of acid gas (hydrogen sulfide) (Step 5) and carbon
monoxide Acid removal usually involves a caustic wash step. The mixed hydrocarbon stream
then goes through additional refining steps (Step 6), where it is separated from olefms (C3 and
lower)
The composition of a typical C4 co-product stream from an ethylene plant using
naphtha feedstocks is shown in Table 4-3.20 The mixed-C4 stream may be sent directly to
butadiene recovery at the same plant. Olefms plants that do not produce finished butadiene may
(1) recover the crude butadiene from the byproduct mixed-C4 streams and sell it to a butadiene
producer, (2) recirculate the stream into the front of the ethylene process, and/or (3) use the
stream to fuel the equipment (e.g., furnaces) in the ethylene process.
4-4
-------
Control
D»vlc»(t)
flfln*t*ll»d)
0
Steam
Cracking
Fumaea
M/xad
Hydrocarbon
hing
Qu
7)
uootuopafjj
auf/oaag
-
e|
Compressor
©
<«>'
'
uaoai
1
Add Oa«
Ramoiral
Otaffna
(Ci and lowtt)
To Raeoirary
Staam
Fuaf
Waste
SCrvam
SCraam to Bulad/ana
Racovary
Proeaaa
Otoffn*
fC< and h/jh»r>
To Rteovtry
TraaCmanf Syttom
(irinatelfadj
Source: Reference 19
Figure 4-1. Process Diagram for Production of a Mixed-C4 Stream Containing Butadiene
t
f
-------
TABLE 4-3. TYPICAL COMPOSITION OF MIXED-C4 STREAM FORMED FROM
NAPHTHA FEEDSTOCK USED TO PRODUCE ETHYLENE*
Component
n-Butane
Isobutane
Isobutene
1-Butene
trans-2-Butene
cis-2-Butene
1,3 -Butadiene
1,2-Butadiene
Propadiene
Methyl acetylene
Ethyl acetylene
Dimethyl acetylene
Vinyl acetylene
TOTAL
Molecular
Formula
C4H10
C4H10
C4H8
C4Hg
CA
C4H8
CA
CA
CA
CA
CA
CA
CA
Composition
(wt. %)
6.80
1.60
29.00
9.60
7.50
4.70
39.30
0.08
0.53
0.65
0.05
0.08
0.11
100.0
Source Reference 20.
* Refer to Figure 4-1 for process diagram of mixed-C4 production.
The second part of this butadiene production process involves recovering the
butadiene from the mixed-C4 stream. A generalized block flow diagram of a butadiene recovery
unit is shown in Figure 4-2.19 The mixed-C4 stream is fed from pressurized storage tanks into a
hydrogen reactor along with hydrogen (Step 1) to convert some of the unsaturated hydrocarbons
such as acetylene to olefins. The product C4 stream from the hydrogenator is combined with a
solvent (typically furfural) and fed into an extractive distillation operation (Step 2). In this
operation, most of the butanes and butenes are separated from butadiene, which is absorbed in
the solvent along with residual impurities. A stripping operation is then used to separate the
butadiene from the solvent.
4-6
-------
Mftntf-C*
Straim A
Irem Ol*fln*
>
H
^
© ©
^-x
<
Aflrjm*
rfrogtiutf
Hydrocarbon
Protfucte
on
I
i
i
(IftottMtkd)
•utonv-BifMni
Strtam (o S(or»0«
11
tt
V
•uea
anrfMc
rfton*
tWu«lt
* -N.
i
!
(e)
VmforUH .
•• Fuel
I
•e
•uMfme
0
( j HTMM Str»m
©
11-^
i
M«Mu*l* M
HjroVogtn
Rtcevtrjr
fc
Source: Reference 19
Figure 4-2. Process Diagram for Butadiene Production by Recovery from a Mixed-C 4 Stream
-------
The stream containing butadiene typically has a small amount of residuals. Some
of these residuals are alkynes that were not converted to olefins in the hydrogenation reactor.
These residuals are removed from the butadiene stream by distillation (Step 3) and are usually
vented to an emissions control device (Vent A). The bottom stream exiting the acetylenes
removal operation contains butadiene and residuals such as polymer and 2-butene. The residuals
are removed in the butadiene finishing operation (Step 4) and sent to a waste treatment system or
recovery unit. The finished butadiene is then stored in pressurized tanks.
Oxidative Dehydrogenation of n-Butenes
The oxidative dehydrogenation of n-butenes (1- and 2-butenes) proceeds through
the following primary reaction:
CH2 - CH - CH2 - CH3
(1-butene)
or + 1/2 O2 > CH2 = CH - CH = CH2 + H2O
CH3 - CH = CH - CH3 (1,3-butadiene)
(2-butene)
Between 2.4 and 2.9 pounds (1.1 and 1.3 kilograms) of n-butenes are consumed per pound
(kilogram) of butadiene formed.
A generalized block flow diagram of the butenes dehydrogenation process is
shown in Figure 4-3.21 A feed stream of n-butenes is combined with steam and air, preheated,
and passed through a dehydrogenation reactor (Step 1). Air is used as a source of oxygen to
remove hydrogen from the butenes feed. The typical composition of a product stream is shown
in Table 4-4.21 The product stream is compressed after exiting the reactor (Step 2) and sent to a
hydrocarbon absorption and stripping process (Step 3). During compression and absorption,
vent streams containing nitrogen, excess oxygen, and volatile organic compounds (VOCs) are
4-8
-------
AT*!*.1 »•/•* Inilcittt ttifl bvudltnt It ant at Hit mtm ctmpontnt*.
Source: Reference 21
Figure 4-3. Process Diagram for Production of Butadiene by the Oxidative Dehydrogenation of Butene
-------
TABLE 4^t. TYPICAL COMPOSITION OF n-BUTENES OXIDATIVE
DEHYDROGENATION REACTOR PRODUCT STREAM3
Component
Oxygen
Nitrogen
Carbon oxides
Water
Methane
C2's
C3's
n-Butane
Isobutane
Isobutene
1 -Butene
trans-2-Butene
cis-2-Butene
1.3 -Butadiene
C5's
1.2-Butadiene
Propadiene
Methyl acetylene
Ethyl acetylene
Dimethyl acetylene
Vinyl acetylene
Molecular
Formula
02
N2
CO, CO2
H2O
CH4
C4H10
C4Hio
C4H8
C4Hg
C4Hg
C4Hg
CA
CA
C4H4
C4H4
C4H4
C4H,
C.H.
Composition
(wt. %)
1.0
15.8
3.0
65.0
0.1
0.3
0.4
0.4
0.6
1.1
1.9
1.7
1.4
7.2
0.1
Trace
Trace
Trace
Trace
Trace
Trace
Source Reference 21.
" Refer to Figure 4-3 for a process diagram of butadiene production by n-butenes oxidative dehydrogenation.
4-10
-------
routed to an incinerator. The overhead stream from the hydrocarbon stripping column (not
shown in Figure 4-3) is routed to a light-ends column for further separation.
The C4 and heavier compounds (labeled hydrocarbons) exiting the
absorption/stripping process are fed to a distillation operation (Step 4), where butadiene is
separated from the unreacted n-butenes. The n-butenes stream exiting the distillation operation
also contains C5 and heavier hydrocarbons. This stream is routed to a separation process
(Step 5), where n-butenes are recovered and recycled to the dehydrogenation reactor.
The stream containing butadiene from the distillation process (Step 4) is routed to
a finishing distillation process (Step 7). At this point, finished butadiene is separated from other
hydrocarbons and sent to pressurized storage. A polymer waste stream generated during the
finishing process is routed to an incinerator. The hydrocarbons are sent to butene separation
process units.
4.1.2 Emissions
Regardless of the process used to produce butadiene, emissions of butadiene at a
production facility may be of five general types: process vent discharges, equipment leaks,
emissions from secondary sources (wastewater, liquid waste, or solid waste discharges), storage-
related releases, and emergency or accidental releases. In Figure 4-1, A through F are process
vents, G represents an emission point after a control device. In Figure 4-2, the process vents are
lettered A through D with E representing an emission point after a control device. In Figure 4-3,
A through F are process vents, G, H, and I are emission points after control devices.
No information about emissions associated with storage or emergency/ accidental
releases is available. Storage vessel discharges may be assumed to be negligible because
butadiene is stored in pressure vessels that have no breathing or working losses. Some losses
during transfer of butadiene are possible if the butadiene is not used on site. However, these
losses should be low because the butadiene has to be transferred under pressure without release
points.
4-11
-------
Emissions are presented in the form of emission factor ranges for process vents
and secondary sources. Individual emission factors having units of pounds (kilograms) of
butadiene emitted per ton (megagram) of butadiene produced were first calculated for each
facility by dividing facility-specific estimates by production, taken as 80 percent of capacity.19
From these facility-specific emission factors, a range for each source was established. The
values of "n" indicate the number of facilities included. Because facilities reported varying
levels of controls, two sets of emission factor ranges were developed. One range reflects actual
facility emissions in which each facility may control all, some, or none of its sources. The
second range incorporates both emissions from existing uncontrolled sources and potential
emissions from controlled sources if controls had not been in place.
Equipment leak emissions are based on equipment count data collected by CMA
in 1989 and average CMA emission factors for butadiene producers.
Facility-specific emissions estimates and capacity data appear in Appendix C,
Tables C-l through C-4. These emission factor ranges and annual emissions should be used
only as order-of-magnitude approximations because differences in production processes and
control levels, among other variables, may significantly influence actual emissions.
Process Vent Discharges
Process vent discharges occur from reactor vessels, recovery columns, and other
process vessels. They may occur continuously (from a continuous process) or intermittently
(from a batch process). Some continuous processes also have intermittent VOC emissions
during startup and shutdown, or during control device malfunction or process upsets.
The possible locations of these process vents are shown in Figures 4-1
through 4-3. The actual locations and butadiene content may vary depending on the particular
facility design. In many cases, process vents are directed to other parts of the plant or to a gas
recovery system for use as fuel rather than discharged to the atmosphere.
4-12
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Emissions data, including the use of control devices (six facilities use flares, of which two also
have fuel gas recovery systems), were available for some facilities (see Appendix C). An
emission factor range derived from these data is presented in Table 4-5. Also included in the
table is an uncontrolled emission factor range to provide an indication of the extent to which
controls are used. These were calculated from controlled emission factors using the emissions
reduction efficiencies listed in Table 4-6.22'23'24 It should be noted that use of these factors
introduces uncertainty. Many flares and incinerators achieve greater than 98 percent control. If
99 percent were used as a factor instead of 98, uncontrolled emissions estimates would double.
Processes for both olefins production and butadiene production via oxidative
dehydrogenation are potential sources of emissions. However, the emissions data are limited to
the olefins process at the two facilities. One of the facilities is reportedly controlling process
vents on the oxidative dehydrogenation process at the hydrocarbon absorbing and stripping
column and at the compressors (incinerator and flare) (see Figure 4-3).
Equipment Leak Emissions
Emissions from process equipment components occur when the liquid or gas
process streams leak from the equipment. These components include pump seals, process valves,
compressors, safety relief valves (pressure relief devices), flanges, open-ended lines, and
sampling connections.
The emissions estimates shown in Table 4-5 are the results of a study conducted
by CMA.25 The study's objective was to develop industry-specific emission factors to replace
SOCMI emission factors26 because the SOCMI emission factors were thought to overestimate
equipment leak emissions for butadiene producers. The study recommends, however, that
screening data and correlation equations (also revised) be used to generate the most accurate
estimates.
4-13
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TABLE 4-5 SUMMARY OF HMISSION FACTORS FOR BUTADIENE PRODUCTION FACILITIES
(FACTOR QUALITY RATING E)
Emission Sources
Process Vents:
C4 stream production
3-01-153
Recovery process
3-01-153-01
Secondary Sources'
Recovery process - \vastewater
3-01-153
Recovery process - solid waste
3-01-153
l-acilit\ Hmission
Range
—
0.0068 - 0 0550 Ib/ton (n=3)
(0 0034 - 0 0275 kg/Mg)
0.00068 - 4.4 Ib/ton (n=6)
(0.00034 - 2.2 kg/Mg)
Negligible" (n=2)
Factors''1"
Mean
—
0.03 14 Ib/ton
(0.0 157 kg/Mg)
0.936 Ib/ton
(0.468 kg/Mg)
—
Uncontrolled Emission Factors"-1"
Range
0.0054 Ib/ton
(0.0027 kg/Mg)
0.0322 - 0.6872 Ib/ton (n=3)
(0.0161 -0.3436 kg/Mg)
—
—
Mean
—
0.4652 Ib/ton
(0.2326 kg/Mg)
-™
Source: References 19 and 25.
Note: Annual emissions from equipment leaks, recovery process (SCC 3-01-153-80), are 455 tons/yr (407 Mg/yr) (n=9)1>Cld
"Assumes production capacity of 80 percent
bFactors are expressed as Ib (kg) butadiene emitted per ton (Mg) produced.
"Ranges are based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
dTotal number of components is 79,430: 60 percent flanges, 29 percent liquid valves, 8 percent gas valves, and 3 percent all others combined.
•Defined as 0.4988 x W6 kg/Mg.
"—" means no data available.
n = number of facilities.
-------
TABLE 4-6. VOC EMISSIONS REDUCTION EFFICIENCIES OF CONTROL DEVICES
USED TO ESTIMATE CURRENT BUTADIENE EMISSIONS
Reduction Efficiency
Control Device" (%) : Reference
Gas recovery (boiler) 99.9 21
Flare 98 22
Incinerator 98 23
1 Devices reported by industry to control vent streams and secondary emissions. Possible placement of
control devices are shown in Figures 4-1 through 4-3.
The Butadiene Panel of CMA designed its study to closely adhere to EPA
protocols for generating unit-specific emissions estimates as specified in the 1987 draft
Protocols for Generating Unit-Specific Emission Estimates for Equipment Leaks of VOC and
VHAP. In addition to using the protocols, the Butadiene Panel sought EPA comments on the
procedure before it began collecting data. Nine of the 11 finished butadiene producers in the
United States participated in the study. The exceptions were the Shell facility in Norco,
Louisiana, which was not in service, and the Texas Petrochemical facility in Houston, Texas.
Four facilities that produce only crude butadiene also contributed data: three Union Carbide
plants in Seadrift, Texas, Taft, Louisiana, and Texas City, Texas; and Dow Chemical in
Freeport, Texas All of these facilities produce butadiene by the recovery process. No estimate
of equipment leak emissions from the oxidative dehydrogenation process was possible because
of the lack of equipment component counts.
Based on facility data, ranges of butadiene concentrations through equipment
components were established. Weighted average percents were calculated from the number of
each component in each range. Approximately 20 percent of components were associated with
butadiene streams having between 5-30 percent concentration, 47 percent with the 30-90 percent
butadiene range, and 33 percent with the 90-100 percent butadiene range.
4-15
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The screening data collected were similarly grouped into ranges of concentration
[parts per million (ppm)] based on the instrument readout and the butadiene concentration in the
stream. Five ranges from 0-9 to >9999 ppm were used. Upon calculating weighted average
percents, about 76 percent of components fell in the 0-9 ppm range and 19 percent in the 10-99
ppm range. Fewer than 6 percent were found to be greater than 100 ppm. Table 4-7
summarizes the study results.25
In addition to average emission rates, average butadiene concentration in the
stream through each type of component is shown. These average concentrations were used to
convert SOCMI emission factors from units of VOC emissions to butadiene emissions for
purposes of comparison to the new emission rates. The results of this comparison are also given
in Table 4-7.
In addition to compiling the data from all facilities, the study analyzed the data on
a plant-specific level. Table 4-8 provides the variability among the plants by component type
determined from this analysis.25
The emissions shown in Table 4-7 include the reduction achieved by the various
controls in place at the 13 facilities. The Butadiene Panel conducted a survey to identify and
evaluate practices in the plants that would contribute to emissions reductions. Of the six
respondents, all stated that they monitor fugitive emissions using a combination of visual
observation and automatic audible alarm for specific equipment such as pumps and compressors.
Three plants have routine leak inspection and maintenance programs. Two plants informally
require immediate repair of leaks detected by the monitoring system. Five of the six plants
reported combinations of visual inspections, pressure testing, VOC monitoring, use of double-
sealed pumps, seals vented to a flare, bubble-testing flanges, tightness testing of valves, use of
special packing material, closed-loop sampling points, and plugging of all open-ended lines. No
estimate of the emissions reductions achieved by these practices was determined.
4-16
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TABLE 4-7. AVERAGE BUTADIENE EMISSION RATES FOR PROCESS EQUIPMENT
COMPONENT LEAKS
Equipment Component
(Emission Source)
Pumps : Liquid
Compressors
Flanges
Valves - Gas
Valves - Liquid6
Pressure Relief Devices
"Safety Valves"
Sampling Pointd
Open-ended Lines
Average Butadiene
Average Emission Rate* Concentration Reduction1"
(Ib/hr/component) (%) (%)
0.05634
(0.02555)
0.000004
(0.0000018)
0.000307
(0.000139)
0.001105
(0.000501)
0.003140
(0.001424)
0.02996
(0.013590)
-
0.000120
(0.000054)
64.1 19.3
27.9 99.9+
61.0 72.5
60.2 85.1
59.7 66.3
56.7 76.9
-
67.9 95.2
Source Reference 25.
" The average emission rate has been derived from facility data, some of whom are using controls. Numbers
in parentheses are in units of kg/hr/component
b Calculated as [1 - CMA emission factor 1 x 100
SOCMI emission factor
c Liquid refers to light liquid and is defined as a petroleum liquid with a vapor pressure greater than the
vapor pressure of kerosene.
d Sampling points were considered to be a subset of open-ended lines; therefore, data were incorporated in
the open-ended line average emission factor
4-17
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TABLE 4-8. VARIABILITY IN FACILITY-SPECIFIC EMISSION RATES FOR
EQUIPMENT LEAKS
Relative Standard Deviation
Equipment Component (%)
Pumps - Liquid 96.0 (n=13)
Compressors 137.4 (n=3)
Flanges 91.4(n=13)
Valves - gas 84.3 (n=13)
Valves - liquid 45.2 (n=13)
Pressure Relief Devices 226.6 (n=10)
Open-ended Lines 117.8 (n=6)
Sample points 102.1 (n=4)
Source: Reference 25.
In the absence of specific information relating controls in use to reduction
achieved, previously developed control efficiencies are presented in Table 4-9 to provide an
indication of typical reductions achieved. For leak detection and repair programs, EPA has
provided a method for estimating the emission reductions in Protocol for Equipment Leak
Emission Estimates1 The reader is referred to this document for this information. To apply
these efficiencies and determine emissions after controls, an estimate of uncontrolled emissions
would be multiplied by [1-(efficiency/100)]. More information on estimating uncontrolled
emissions is provided in Appendix D.
4-18
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TABLE 4-9. CONTROL TECHNIQUES AND EFFICIENCIES APPLICABLE TO
EQUIPMENT LEAK EMISSIONS
Equipment Type
Approximate Control
Modification Efficiency (%)
Pumps
Compressors
Pressure relief devices
Valves
Connectors
Open-ended lines
Sampling connections
Sealless design
Closed-vent system
Dual mechanical seal with barrier fluid
maintained at a higher pressure than the
pumped fluid
Closed-vent system
Dual mechanical seal with barrier fluid
maintained at a higher pressure than the
compressed gas
Closed-vent system
Rupture disk assembly
Sealless design
Weld together
Blind, cap, plug, or second valve
Closed-loop sampling
100a
90b
100
90b
100
100
100a
100
100
100
Note Based on Reference 1 Butadiene emissions were assumed to be reduced by the same percentage as VOC
emissions
" Sealless equipment can be a large source of emissions in the event of equipment failure.
b Actual efficiency of a closed-vent system depends on percentage of vapors collected and efficiency of control
device to which the vapors are routed.
c Control efficiency of closed-vent systems installed on a pressure relief device may be lower than other closed-vent
systems, because they must be designed to handle both potentially large and small volumes of vapor.
4-19
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Secondary Emissions
Secondary emissions occur during the treatment and disposal of wastewater, other
liquid waste, and solid waste. Few emissions estimates are available, and most of these data
pertain to wastewater from the butadiene recovery process. Table 4-5 summarizes emission
factors derived from the estimated wastewater and solid waste emissions in Appendix C. No
factors are available for the olefins process, the oxidative dehydrogenation process, or for any
liquid waste other than wastewater. The types of waste streams generating butadiene emissions
include cooling water, wash water, solvent recovery wastewater, process unit wastewater, and
waste polymer.
Because of its volatility and low solubility in water, butadiene in a waste stream is
assumed to completely volatilize unless the vapor is routed to a control device. Some facilities
use such emission control systems; others do not. Available information on facility control
status and handling of the waste streams in 1984 is summarized in Appendix C.
4-20
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SECTION 5.0
EMISSIONS FROM MAJOR USES OF BUTADIENE
Emissions from industrial processes using butadiene as a raw material are
discussed in this section. Butadiene has six primary commercial uses, as illustrated in the
chemical use tree in Figure 3-1. These uses are the production of styrene-butadiene (SB)
copolymer, polybutadiene, adiponitrile, neoprene, acrylonitrile-butadiene-styrene (ABS)
copolymer, and nitrile elastomer.
This section includes a subsection for each major use. Each subsection provides a
general discussion of the production process, estimates of the associated butadiene emissions,
and a description of any existing emissions control practices. These discussions are primarily
based on summary memoranda of industry responses to EPA Section 114 questionnaires,
National Institute for Occupational Safety and Health (NIOSH) survey reports, and various other
reports as referenced, and represent information gathered prior to 1986. The level of detail
varies according to the availability of information. In view of these limitations, the reader is
advised to contact individual facilities or review State permit files for more complete and
accurate information.
As with butadiene production sources, emission factor ranges in units of pounds
(kilograms) butadiene emitted per ton (megagram) produced are provided for process vents and
secondary sources, based on annual emissions estimates of tons/yr (Mg/yr). The same procedure
described in Section 4.0 for calculating facility emission factors was followed to establish these
ranges. Assumptions about production are provided in each subsection.
5-1
-------
Equipment leak emissions are presented as annual emissions and were derived
using the procedure in Appendix D and the CMA emission factors presented in Section 4.0.
Although developed for butadiene producers, these emission factors were assumed to better
represent practices of the user industries because all involve butadiene handling. Three
alternative methods would be to (1) collect screening data and use correlation equations
established in the CMA work, (2) apply SOCMI emission factors, weighted for the percent
butadiene in the stream, or (3) apply other alternatives identified in the EPA document 7995
Protocols for Equipment Leak Emission Estimates.1 The equipment leak emission estimates
generally represent some level of control because the average emission rate is based on practices
at butadiene producers.
The emission factors and annual emission values should be used only as estimates
because facilities did not always provide complete information, and source characteristics cannot
be assumed to be the same from location to location. The number of facilities included in
establishing the range is indicated in parentheses; the individual values are reported in
Appendix C.
Company identification and corresponding facility locations for the various
production process are also given in each subsection. The production capacities supplied are, in
most cases, taken from more recent (1992-1993) references.
5 1 STYRENE-BUTADIENE COPOLYMER PRODUCTION
Styrene-butadiene copolymers are composed of the monomer units butadiene and
styrene Depending upon the feed composition and extent of drying in the process, SB
copolymers can be a solid or an emulsion.
Copolymers of styrene and butadiene that contain over 45 percent butadiene have
rubber-like properties. The copolymers become more plastic-like when the styrene content is
increased to above 45 percent.27 Copolymers with more than 45 percent butadiene are
sometimes referred to as styrene-butadiene rubber (SBR); products with more styrene may be
5-2
-------
referred to as SB latex. No distinction is made in the following discussion because emissions
data are not differentiated. The term elastomer will be used in a generic sense, meaning solid
copolymer.
Styrene-butadiene latex is an elastomer emulsion. Styrene-butadiene rubber is
also used as an emulsion. The emulsion process is the same process used for elastomers, except
that it lacks the emulsion breaking (coagulation) and drying steps. The term latex is used here
when referring to both SB and SBR emulsion.
Styrene-butadiene copolymers account for 40 percent of national butadiene
consumption.8 The majority of SB elastomer produced is used by the tire industry. Latex has a
wider variety of uses in industries such as textiles, paper, and adhesives manufacturing.
5.1.1 Process Description
Elastomer is manufactured by two processes: (1) the emulsion process, where
monomer is dispersed in water, and (2) the solution process, where monomer is dissolved in a
solvent. The emulsion process is more commonly used. Latex is similarly produced but is
removed prior to the final processing that generates the solid copolymer.
A generalized block flow diagram of an elastomer and latex production process is
shown in Figure 5-1 27 Stored butadiene and styrene monomers are first washed to remove any
inhibitors of the polymerization reaction (Step 1). The scrubbed monomers are then fed into
polymerization reactors (Step 2) along with the ingredients listed in Table 5-1,28 After the
polymerization reaction has progressed to the desired extent, a polymer emulsion (latex) is
removed from the reactors along with unreacted monomer (Step 3). Both styrene and butadiene
are separated from the latex and recycled to the monomer feed tanks.
5-3
-------
IE)
*
Control
Devlce(s)
(If installed)
Vent or Pressure Relief |
!AJ
I
^
t
\
S-'
P-
,--t-N ^^ Butadiene Recycle ^
Butadiene^ "i ,_ _
Storage j ^
Y
-r
Styrene
Storage
4
i
t
—
'
Source. Reference 27 Figure 5-1. Process Diagram for Production
>
Blending
uoaguiauon
<
Finished
Latex
/\
of SB Copolymer
Washing
and
Drying
- oiyrono-
Butadiene
Rubber
nr
Elastomer
t
J
S
i
-------
TABLE 5-1. TYPICAL RECIPE FOR EMULSION SBR
Components
Butadiene
Styrene
d-Isopropyl Benzene Hydroperoxide
Ferrous Sulfate
Tert-Dodecyl Mercaptan
Potassium Pyrophosphate
Rosin Acid Soap
Water
Weight Percent
25.0
10.0
< 1
<1
.1
.1
1.4
63.0
Function
Monomer
Monomer
Catalyst
Activator
Modifier
Buffer
Emulsifier
Source: Reference 28.
The unfinished latex may take one of two routes after monomer is removed. One
route is for the latex to be blended into a homogenous emulsion (Step 4) and stored as finished
latex. The other route involves a coagulation operation where the emulsion is broken (Step 5).
This step is followed by washing and drying the polymer into a solid form (Step 6).
Table 5-2 lists the known production facilities, grouped by copolymer type29
Because three different latexes may be produced-SBR, SB, and styrene-butadiene-vinylpyridine
(SBV)--the table indicates which copolymer(s) each facility manufactures.
5.1.2 Emissions
The emission sources at an SB copolymer facility are typical of those common to
chemical production facilities: process vent discharges; equipment leaks; wastewater, liquid
waste, or solid waste discharges (secondary emissions); storage-related releases; and accidental
or emergency releases. Available emissions data are limited to emissions from process vents,
equipment leaks, and secondary emissions, and are shown in Tables C-5 through C-8
5-5
-------
TABLE 5-2. STYRENE-BUTADIENE ELASTOMER AND LATEX
PRODUCTION FACILITIES
Company
Location
Capacity in 1993
tons/yr (Mg/yr)
Elastomer
Ameripol Synpol
Copolymer Rubber
Dynagen, Inc.
Firestone
Goodyear
Goodyear
Latex
PortNeches.TX
Baton Rouge, LA
Odessa, TX
Lake Charles, LA
Houston, TX
Beaumont, TX
372,200 (335,000)
138,900(125,000)
100,000 (90,000)
166,600(150,000)
338,900 (305,000)
22,200 (20,000)
Type of Latex
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Dow Chemical U.S. A.
GenCorp
GenCorp
Goodvear
(ioochear
lu>od\ ear
1 lamp.shire Chemical Corp
BASF
BASF
Reichhold Chemicals, Inc.
Reichhold Chemicals, Inc.
Rhone-Poulenc, Inc.
Rhone-Poulenc, Inc.
Rhone-Poulenc, Inc.
Rhone-Poulenc, Inc
Dalton, GA
Freeport, TX
Gales Ferry, CT
Midland, MI
Pittsburg, CA
Howard, WI
Mogadore, OH
Akron, OH
Calhoun, GA
Houston, TX
Owensboro, KY
Monaca, PA
Chattanooga, TN
Cheswold, DE ]
1
Kensington, GA 1
Gastonia, NC
Charlotte, NC
La Mirada, CA
Kankakee, IL
252,200 (227,000)
40,000 (36,000)
101,100(91,000)
4,400 (4,000)
55,500 (50,000)
28,900 (26,000)
14,400(13,000)
25,500 (23,000)
115,500(104,000)
> 93,300 (84,000)
25,600 (23,000)
30,000 (27,000)
13,300(12,000)
10,000(9,000)
SB latex
SB latex
SB latex;
SBR latex;
SBV latex
SB latex;
SBV latex
SB latex;
SBR latex;
SBV latex
SBR latex
SB latex
SB latex
SB latex;
SBR latex
SB latex
SB latex
SB latex
SB latex
SB latex
Source Reference 29
5-6
-------
in Appendix C. In developing emission factors, the facilities were assumed to be operating at
80 percent production capacity.27
Butadiene used in elastomer production is usually stored in pressurized vessels
with some vented to a flare (point A in Figure 5-1). Storage, therefore, results in low emissions.
Two facilities, however, store butadiene-containing material in fixed-roof storage tanks.
Emissions are estimated to be low because of the low concentrations of butadiene (5 percent by
weight or less).
Butadiene users do not transfer butadiene as a product onto tank trucks, so
emissions from transfer operations are not of concern. Unloading emissions would be mostly
emitted as storage tank working losses (already discussed under storage). Moving butadiene
around within the plant is covered by equipment leak emission estimates.
Process Vent Emissions
As seen from the vent locations in Figure 5-1, process vent discharges occur from
reactor vessels, recovery columns, and other process vessels. They may occur continuously
(from a continuous process) or intermittently (from a batch process). Some continuous
processes have emissions during startup and shutdown or during a control device malfunction or
process upset.
The potential locations of these process vents (Vents B, C, D, F) are shown in
Figure 5-1 Although the actual locations and butadiene content may vary depending on the
facility design, process vents are typically located on absorption columns used to recover
butadiene. In some cases, process vents are directed to other parts of the plant, or to a gas
recovery system for use as fuel, rather than discharged to the atmosphere.
The available emissions data are presented in Table 5-3 as emission factor ranges.
The facility emission factor range was calculated as described in Section 4.0 and reflects actual
5-7
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TABLE 5-3. SUMMARY OF EMISSION FACTORS FOR SB COPOLYMER PRODUCTION FACILITIES3'1'
(FACTOR QUALITY RATING D)
Emission Sources
Facility Emission Factors
Uncontrolled Emission Factors
Range0
Mean
Range
Mean
00
Process Vents
3-01-026
Secondary Sources:
Wastewater
3-01-026
Other liquid waste
3-01-026
Solid waste
3-01-026
0.00024 - 94.34 Ib/ton 7.10 Ib/ton
(n=18)
(0.00012-47.17 kg/Mg) (3.55 kg/Mg)
0.124 - 94.34 Ib/ton (n=18) 14.20 Ib/ton
(0.062 - 47.17 kg/Mg) (7.10 kg/Mg)
0 - <10 Ib/ton (n= 18)
(0-<5kg/Mg)d
O.02 Ib/ton (n=5)
(<0.01 kg/Mg)
0-<0.02 Ib/ton (n= 11)
(0-<0.01 kg/Mg)d
0.30 Ib/ton
(0.15 kg/Mg)
<0.02 Ib/ton
(<0.01 kg/Mg)
<0.02 Ib/ton
<0.01 kg/Mg
Source: Reference 27
Note: Annual emissions from uncontrolled equipment leaks range 0.11 - 23.59 tons/yr (0.10 - 21.40 Mg/yr) and average 7.28 tons/yr (6.60 Mg/yr) (n=19).'
* Assumes production capacity of 80 percent.
b Factors are expressed as Ib (kg) butadiene emitted per ton (Mg) produced
c Ranges are based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
d Upper value used to prevent disclosing confidential operating capacity.
n = number of facilities.
NA = not available
"—" means no data specific to level or efficiency of controls were available
-------
emissions and the various levels of control reported. The second emission factor range
incorporates both emissions from existing uncontrolled sources and potential emissions from
controlled sources with controls removed.27
Although 20 facilities supplied emissions data (Table C-6), production capacities
for two were not available; therefore, these two were omitted from the emission factor range
development. Control devices in use include absorbers, boilers, flares, scrubbers, and pressure
condensers. Emissions after controls (Vent E) were calculated by applying appropriate
reduction efficiencies. Standard control efficiencies from Table 4-6 were used to calculate
controlled emissions unless alternate values were supplied by the companies and accompanied
by quantitative documentation.
Equipment Leak Emissions
Emissions occur from process equipment components whenever the liquid or gas
process streams leak from the equipment. Butadiene emissions were estimated for the following
equipment components: pump seals, process valves, compressors, safety relief valves (pressure
devices), flanges, open-ended lines, and sampling connections. For each facility where the
number of equipment components was known, emissions were estimated using emission rates
presented in Table 4-7. The method is described further in Appendix D. Although these
emission rates include an unknown level of control at butadiene producer, the only controls
reported in use by the industry are flares and/or rupture discs for pressure relief devices (PRD).
Some facilities perform visual inspections, but with an unknown frequency. These estimates
may not represent emissions at SB copolymer facilities where control practices differ. A
summary of the available data is given in Table 5-3.
Secondary Emissions
Secondary emissions occur at the on-site and off-site facilities that treat and
dispose of wastewater, liquid waste, or solid waste. Waste streams may be generated from any
of the operations shown in Figure 5-1. Emissions data are available for 18 of the 21 facilities,
5-9
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TABLE 5-4. POLYBUTADIENE PRODUCTION FACILITIES
Capacity in 1993
Company Location tons/yr (Mg/yr)
American Synthetic Rubber Louisville, KY 12l,300a (110,000)"
Bridgestone/Firestone Orange, TX 132,300 (120,000)
Bridgestone/Firestone Lake Charles, LA —b
Goodyear Beaumont, TX 237,000* (215,000)'
Polysar Orange, TX 126,800(115,000)
Source: References 12 and 30.
" Total includes some multipurpose SBR.
b Facility coproduces SB elastomer and polybutadiene rubber, but is primarily dedicated to SB elastomer.
but are incomplete for each type of waste stream. These data are summarized in Table 5-3. The
emission factor estimates were calculated from information on the flowrate of butadiene
(kg/day) in the stream and facility production. Because of butadiene's volatility and low
solubility, no reduction was included unless butadiene vapors were routed to a control device.
5 2 POLYBUTADIENE PRODUCTION
Polybutadiene production consumes approximately 20 percent of the butadiene
produced.8 Like SB elastomer, polybutadiene is primarily used by the tire manufacturing
industry, but also finds uses in the high-impact resins industry.
Four companies at five U.S. locations currently have the capacity to produce
polybutadiene, two of which coproduce polybutadiene with SB copolymer. These four
companies are listed in Table 5-4.12'30 Firestone in Lake Charles is primarily an SB copolymer
producer, therefore emissions from this facility were included in the preceding section. Only
emissions attributed to the polybutadiene production process are presented in this section.
5-10
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5.2.1 Process Description
The polymerization of butadiene can yield several isomeric polymers. The two of
commercial significance are the cis-1,4 isomer and, to a much lesser extent, the 1,2 isomer.31
The majority of polybutadiene is produced by a solution polymerization process. Smaller
quantities are produced by an emulsion polymerization process. The relative proportions of the
isomers formed are dependent on the catalyst system used and reaction conditions.
The cis-polybutadiene rubber process consists of five basic steps: (1) butadiene
and solvent purification, (2) reaction, (3) concentrations, (4) solvent removal, and (5) drying and
packaging. Figure 5-2 shows a diagram of this process.31 In Step 1, feed butadiene is dried and
combined with a recycled butadiene stream. Solvent, typically hexane or cyclohexane, is also
dried along with a recycled solvent stream. In Step 2, these streams are fed to the reactor, where
polymerization takes place. With solution polymerization, a catalyst, such as lithium, sodium, or
potassium, is used. The overall conversion of the process is greater than 98 percent.31
Reactor effluent is fed to the concentrator (Step 3), where any unreacted
butadiene is removed for recycling. The product stream leaving the concentrator consists of
polybutadiene dissolved in solvent, and is often referred to as "cement." The cement stream
leaving the concentrator contains negligible butadiene. In Step 4, the cement is stripped of
solvent, which is recycled to solvent purification. Stripping occurs through direct steam contact.
The resulting polybutadiene crumb/water stream is dried, compressed, and packaged in Step 5.
This process is run both continuously and in batch mode, but the majority of facilities operate
continuously.
5.2.2 Emissions
Butadiene emissions from polybutadiene production are primarily of four types:
process vent emissions, equipment leaks, secondary emissions, and accidental or emergency
releases. Storage under pressure significantly reduces any potential for storage emissions
5-11
-------
I
*—•*
KJ
f
Control
Device(s)
(If Installed)
Vent or |
Pressure /^\ ^
Relief ^ ^
i Water
1-^ t ' L
/Butadiene\ Drying and/or Butadiene r-J Butadle
V Storage y X\ Purification " Recyc
T^ <2> 1
, 1 |
Polymerization m
Water ^ Reactor ^\,
f t C^'
Solvent Drying and/or Dry
Purification Solvent
/~\'
•o -^
n« S c
" © !.! ©
11 '1
I oo.,
1
L 1
Concentrator ^ Solvent ^ ^ Drying and Polybutadiene
^N, Removal Packaging Rubber
I
Steam
Solvent Recycle
*
Source: Reference 31
Figure 5-2. Process Diagram for Production of Polybutadiene Rubber
-------
(point A in Figure 5-2), although source emissions during handling and transport of raw material
are possible. Each emission type is discussed separately below. Typical production for the
industry is estimated at 81 percent of capacity.31 This is incorporated into the emission factor
calculations.
Process Vent Emissions
Process vent emissions occur during purging of noncondensible gases from
reactors and other process vessels. The emissions may occur continuously or intermittently.
Emission points indicated in Figure 5-2 as Vents B through F give the possible vent locations for
butadiene releases. Emissions after the control device are denoted as Vent G in the process
diagram.
Data on 1984 emissions, both uncontrolled and controlled, and the control type
and efficiency are available for each facility and are summarized as emission factor ranges in
Table 5-5 (for raw data, see Tables C-9 and C-10 in Appendix C). The two ranges were
developed to represent actual emissions, where existing controls are taken into account, and
potential emissions, where all reported sources are treated as uncontrolled sources.
In 1984, all facilities but one were controlling process vent emissions. Four used
at least a flare, and one also used a butadiene absorber. The fifth used a butadiene recovery
system Two facilities reported control efficiencies greater than 98 percent; however, 98 percent
was used as an upper limit in the absence of test data to support the higher numbers.
Equipment Leak Emissions
Equipment leak emissions were estimated by using the number of components,
their time in service, and the weight percent butadiene in the stream. Estimated emissions were
derived by applying the CMA method described in Appendix D to the facility-specific data
5-13
-------
TABLE 5-5. SUMMARY OF EMISSION FACTORS FOR POLYBUTADIENE PRODUCTION FACILITIES"-"
(FACTOR QUALITY RATING U)
Emission Sources
Process Vents
3-01-026
Secondary Sources:
Wastewater
3-01-026
Solid Waste
3-01-026
Facility Emission
Range0
0.00008 - 36.06 Ib/ton (n=6)
(0.00004- 18.03kg/Mg)
0-0.741b/ton(n=3)
(0-0.38kg/Mg)
0 Ib/ton
(0 kg/Mg)
Factors
Mean
6. 14 Ib/ton
(3. 07 kg/Mg)
0.24 Ib/ton
(0.1 2 kg/Mg)
0 Ib/ton
(0 kg/Mg)
Uncontrolled Emission
Range
0.0032 - 36.06 Ib/ton (n=6)
(0.0016- 18. 03 kg/Mg)
0-0.74 Ib/ton
(0 - 0.38 kg/Mg)
0 Ib/ton
(0 kg/Mg)
Factors
Mean
8.96 Ib/ton
(4.48 kg/Mg)
0.24 Ib/ton
(0.12 kg/Mg)
0 Ib/ton
(0 kg/Mg)
Source: Reference 31.
Note: Annual emissions from uncontrolled equipment leaks range from 4.04 - 31.42 tons/yr (3.66 - 28.50 Mg/yr) and average 10.41 tons/yr (9.44 Mg/yr) (n=6)." For
the facilities that reported emissions, none control equipment leaks.
" Assumes production capacity of 81 percent.
b Factors are expressed as Ib (kg) butadiene emitted per ton (Mg) produced
c Ranges are based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
n = number of facilities.
-------
given in Appendix C, Table C-l 1, and component-specific emission factors from Table 4-7.
These results are summarized in Table 5-5. They represent some level of control because the
average emission rate is based on practices at butadiene producers. Although some facilities
perform visual monitoring, none gave a specific frequency or scope of these programs; therefore,
no estimate of reductions could have been made. A comparison to practices at butadiene
producers was also not possible; therefore, users of the estimate should take this uncertainty into
account.
Secondary Emissions
Only one facility reported a wastewater stream containing butadiene. Complete
evaporation of butadiene from this stream, which is sent to a lagoon, was assumed because of
butadiene's volatility and low water solubility. Secondary emissions are summarized in
Table 5-5. One other facility reports that its wastewater contains no butadiene and, therefore,
produces no emissions. One of the three facilities that indicated that they generate solid waste
estimated that no butadiene emissions are released. Table C-12 in Appendix C summarizes the
facility-specific data.
Accidental Release Emissions
Accidental release emissions include pressure relief events and accidental
releases Two of the four facilities reported no accidental release emissions; each of the other
two facilities reported one accidental release. In the first case, the release was a result of a
cracked valve; in the second, a loose flange. The estimated losses were 2,998 pounds (1,360 kg)
over 30 hours and 11 pounds (5 kg) over 5 minutes, respectively.32
5-15
-------
5.3 ADIPONITRILE PRODUCTION
Adiponitrile (hexanedinitrile) is primarily used as an intermediate in the
manufacture of hexamethylenediamine (HMDA) (1,6-diaminohexane), a principal ingredient in
nylon 6,6 production.33 Three facilities currently produce adiponitrile; Table 5-6 identifies their
locations and capacities.29 Only two facilities use butadiene, accounting for 12 percent of
butadiene use in the United States.10 Monsanto uses acrylonitrile as the starting material and is,
therefore, not a source of butadiene emissions and is omitted from further discussion.
5.3.1 Process Description
Both facilities that use butadiene run the adiponitrile process on a continuous
basis. A generalized process diagram (Figure 5-3) illustrates the steps in adiponitrile
production.34 Butadiene is first converted to pentenenitriles by the addition of hydrogen cyanide
in the presence of a catalyst (Step 1). The resulting pentenenitriles stream then continues
through the butadiene column (Step 2) and catalyst removal (Step 3). The intermediary may be
sold commercially or refined further. On-site processing begins with distillation of the
pentenitriles for use in dinitrile synthesis (Step 4). In the dinitrile system unit (Step 5), the
mononitriles are further hydrocyanated for conversion to dinitriles. The resulting mixture of six-
carbon dinitriles is refined by distillation (Step 6). The final product, adiponitrile, is stored in
tanks and then pumped via pipeline to the HMDA unit for hydrogenation. Most of the by-
products of the process are burned in a boiler to recover their heating value. One of the
mononitrile by-products is sold as a commercial product.
5.3.2 Emissions
From facility information, the sources of butadiene emissions are associated with
production up to the point of catalyst removal. Test data of the butadiene column bottoms (at
one location) show less than 0.02 percent by weight of butadiene.34 The emission source types
for which there are data include the process vents (denoted Vents B and C in Figure 5-3),
equipment leaks, secondary sources, and one estimate of losses during butadiene storage railcar
5-16
-------
TABLE 5-6. ADIPONITRILE PRODUCTION FACILITIES
Capacity in 1993
Facility Location tons/yr (Mg/yr)
DuPont Orange, TX 244,400 (220,000)
DuPont Victoria, TX 238,900(215,000)
Monsanto3 Decatur, GA 228,900 (206,000)
Source: Reference 29.
" Monsanto does not use butadiene as a raw material.
unloading at the facility. Other typical sources include emergency or accidental releases and
emissions associated with butadiene storage (Vent A). No data are available for accidental
releases and, because butadiene is stored under pressure, storage losses are assumed to be a small
source of emissions. In order to develop emission factors, production values were needed. In
the absence of facility-specific information, 80 percent of literature capacity values were
assumed to represent production.35
Process Vent Emissions
The emissions reported by the two facilities for process vents are given in
Table 5-7 as emission factor ranges. AJ1 are controlled either by using a flare or by routing
emissions to a boiler (see Tables C-13 and C-14 in Appendix C). Thus, facility emission factors
represent controlled emissions. The uncontrolled emission factors represent potential emissions
for the sources reported. Flares were assigned a 98-percent maximum removal efficiency unless
supplementary data supported higher efficiencies. Because butadiene content in the process
beyond the catalyst removal stage is low, emissions from process vents downstream of this stage
were expected to be negligible.
5-17
-------
To Sump System
HCN —
To Boiler
I
Separator,
Molecular
Sieve
~
-------
TABLE 5-7 SUMMARY OF [{MISSION FACTORS FOR ADIPONITRILE PRODUCTION FACILITIES''1'
(FACTOR QUALITY RATING U)
Emission Sources
Process Vents
3-01-254
Secondary Sources
3-01-254
Facility Emission Factors
Range' Mean
0.121b/ton(n=2) 0.121b/ton
(0.06 kg/Mg) (0.06 kg/Mg)
0.016 - 0.024 Ib/ton (n=2) 0.02 Ib/ton
(0.008 - 0.012 kg/Mg) (0.01 kg/Mg)
Uncontrolled Emission Factors
Range Mean
5.84 - 6.30 Ib/ton (n=2) 6.08 Ib/ton
(2.92 -3.15 kg/Mg) (3.04 kg/Mg)
0.016 - 0.024 Ib/ton (n=2) 0.02 Ib/ton
JU008 - 0.012 kg/Mg) (0.01 kg/Mg)
Source: Reference 35.
Note: Annual emissions from uncontrolled equipment leaks (SCC 3-01-254-20) range 2.72 - 5 25 tons/yr (2.47 - 4.76 Mg/yr) and average 3.99 tons/yr (3.62 Mg/yr)
(n=2)/-b
" Assumes production capacity of 80 percent
b Factors are expressed as Ib (kg) butadiene emitted per ton (Mg) produced. Only incomplete data on emissions were available, therefore, values
underestimate emissions.
c Ranges are based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
n = number of facilities.
NA = not available.
-------
Equipment Leak Emissions
Equipment leak emissions were estimated by using the number of components,
their time in service, and the weight percent butadiene in the stream. Estimated emissions were
derived by applying the CMA method described in Appendix D to the facility-specific data
given in Appendix C, Table C-l 1, and component-specific emission factors from Table 4-7.
These results are summarized in Table 5-7. They represent some level of control because the
average emission rate is based on practices at butadiene producers. Controls in use by the two
facilities include ambient monitoring, quarterly leak detection and repair, double mechanical
seals, and pressure relief devices, some of which are routed to a flare. No comparison to
practices at butadiene producers is possible, however, so the user of the estimate should take this
uncertainty into account.
Other Emissions
Although both facilities list various secondary sources, only two of the emission
values are given, one for wastewater, the second for a waste tank (see Table C-16 in
Appendix C). Emissions from these sources are reported to be uncontrolled. Other secondary
sources reported include butadiene separator blowdown water, waste liquids, and a sump tank.
Emissions from the latter two are routed to a boiler. Another source identified is the unloading
of a storage railcar with a closed vapor balance system, estimated to emit 9.6 tons/yr
(8.7 Mg/yr).
5.4 NEOPRENE PRODUCTION
Neoprene, also called polychloroprene, is a product of chloroprene
(2-chloro-l,3-butadiene) polymerization. Consuming approximately 5 percent of butadiene
produced,8 neoprene rubber is primarily used in the automotive industry in such applications as
belts, cables, hoses, and wires.36 Three facilities currently produce neoprene; these are listed in
Table 5-8, along with 1993 capacities.29 Only two facilities use butadiene as a raw material.
5-20
-------
TABLE 5-8. CHLOROPRENE/NEOPRENE PRODUCTION FACILITIES
Capacity in 1993
Company Location tons/yr (Mg/yr)
DuPont Louisville, KY3 ]
[ 151,100(136,000)
DuPont La Place, LA J
Polysar Houston, TX 30,000 (27,000)
Source: Reference 30.
"This facility does not use butadiene as the raw material. The facility also has an additional 44,000 tons
(39,900 Mg) of idle capacity, which does not use any butadiene either.
Because the DuPont plant in Louisville, Kentucky, starts with chloroprene, it is not included in
the subsequent discussion of process and emissions information.29
5.4.1 Process Description
The production of neoprene is a continuous process that starts with the
chlorination of butadiene to form chloroprene. Figure 5-4 shows this process schematically.37
The initial chlorination (Step 1) takes place in a vapor-phase reactor. This produces a mixture of
3,4-dichloro-l-butene (3,4-DCB) and the cis and trans isomers of l,4-dichloro-2-butene (1,4-
DCB), along with unreacted butadiene. The next process step (Step 2) involves the
isomerization of 1,4-DCB to 3,4-DCB and the removal of any unreacted butadiene. This is
performed in a combined reactor/distillation column under reduced pressure and the presence of
a catalyst. Butadiene is recycled to the chlorinator and 1,4-DCB can be recycled or used
elsewhere.
The final steps in the synthesis of chloroprene involve the dehydrochlorination of
3,4-DCB in a solution of sodium hydroxide and water (Step 3) and further refining (Step 4).
The chloroprene is isolated from the unreacted 3,4-DCB, which is recycled to the reactor. The
overall chemical yield of chloroprene is generally greater than 95 percent.38
5-21
-------
to
Control Devicg(s)
(If installed)
Chlorine
Butadiene
1®
f
I— Sodium Hydroxide
i—Water
DCB Refining/
Isomorization
Chloroprene
Refining
1,4-DCB
to Other Use
or Recycle
DCB = Dichlorobutenee
1,4-DCB = 1,4-Dlchloro-2-Butene
3,4-DCB = 3,4-Dichloro-1 -Butane
Chloroprene to
Polymerization
K
4
Source: Reference 37
Figure 5-4. Process Diagram for Production of Chloroprene Monomer
-------
The chloroprene produced is then used in the production of neoprene elastomers.
A schematic of this process is shown in Figure 5-5.39 Chloroprene proceeds to emulsifi cation
(Step 1), then to initiation, catalysis, and monomer conversion in Step 2. The polymer continues
with short-stopping and stabilization, monomer recovery, and polymer isolation. The resulting
latex can be sold as product or dried and compressed to form neoprene rubber.39
5.4.2 Emissions
Of the five general emission types, information is only available for three:
process vent releases, equipment leaks, and emergency and accidental release emissions. These
sources are discussed in more detail below. Although secondary sources and storage-related
emissions were not characterized, butadiene emissions from pressurized storage tanks were
assumed to be negligible. Some losses during transfer and handling are likely. For purposes of
emission factor development, both facilities were assumed to be operating at full capacity.39
Process Vent Emissions
The two facilities using butadiene report that process vent emissions are limited
to the chloroprene production process. These vents are associated with the chlorination, DCB
refining, and isomerization steps (identified as Vents A and B in Figure 5-4) and are used to vent
noncondensible gases such as nitrogen. Unreacted butadiene is removed after chlorination is
complete and, therefore, is only present in low quantities in subsequent process steps. A
summary of the data collected in 1985 appears in Table 5-9. The raw data are shown in
Tables C-17 and C-18 in Appendix C. Calculated as described in Section 4.0, the facility
emission factor range reflects the use of some controls by both facilities. The uncontrolled
emission factor ranges represent potential emissions if the sources reported were not controlled.
5-23
-------
Water
Emulsifiar
to
Dry Latex
to Bagger
8
5
Source: Reference 39
Figure 5-5. Flow Sheet for the Production of Neoprene
-------
TABLE 5-9 SUMMARY OF EMISSION FACTORS FOR NEOPRENE PRODUCTION FACILITIES*"
(FACTOR QUALITY RATING E)
Emission Sources
Process Vents
3-01-026
Secondary Sources
3-01-026
Facility Emission Factors
Range0 Mean
0.32 - 6.78 Ib/ton (n=2) 4.04 Ib/ton
(0.16-3.89kg/Mg) (2.02kg/Mg)
NA . NA
Uncontrolled Emission Factors
Range Mean
0.40 - 24. 18 Ib/ton (n=2) 12.28 Ib/ton
(0.20 - 12.09 kg/Mg) (6.14 kg/Mg)
NA NA
Source: Reference 39.
Note: Annual emissions from uncontrolled equipment leaks range 1.03 - 4.88 tons/yr (0.93 - 4.43 Mg/yr) and average 2.95 tons/yr (2.68 Mg/yr) (n=2).' For the
facilities that reported emissions, none control equipment leaks.
V " Assumes production capacity of 100 percent.
ui b Factors are expressed as Ib (kg) butadiene emitted per ton (Mg) produced.
c Ranges are based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
n = number of facilities.
NA = not available.
-------
Both facilities use controls, but the water-cooled condenser at one facility affords
no emissions reduction. Also, the control efficiency of a flare in use was assigned a 98-percent
removal efficiency, despite a higher value reported, because of the lack of supporting test data.
Emissions from control devices are identified as Vent C on the process diagram.
Equipment Leak Emissions
Using facility-supplied information on the number of equipment components and
the CMA procedure in Appendix D, equipment leak emissions estimates were calculated (see
Table C-18 in Appendix C) and are summarized in Table 5-9. Although both facilities perform
visual and area monitoring, neither provided specific information about these programs. No
other controls were reported to be in use. The estimates include some level of control because
the average emission rates are based on practices at butadiene producers.
Short-term Emissions
As a result of specific requests by the EPA for emissions data, short-term
emissions are relatively well characterized. The data fall into four categories: short-term
process vent emissions, pressure relief events, short-term emissions from equipment openings,
and emissions from accidental releases.37 No emissions were routed to a control device. A
summary of the estimated emissions is given in Table 5-10.37 Additional emissions are possible
because companies were only asked to report the larger releases for that year.
5 5 ACRYLONITRILE-BUTADIENE-STYRENE COPOLYMER PRODUCTION
Acrylonitrile-butadiene-styrene (ABS) resins are currently produced by four
companies at 10 locations.14 Table 5-11 presents a list of these facilities with their approximate
capacities.29 At least four of the ten facilities producing ABS do not use butadiene. They start
instead from polybutadiene and proceed either through the suspension process or the continuous
mass process. Therefore, no butadiene emissions are expected from these production processes.
5-26
-------
TABLE 5-10. SHORT-TERM EMISSIONS FROM NEOPRENE PRODUCTION FACILITIES
Facility
Event Description
Number of Amount
Events Duration Released per
per Year (minutes) Event Ib (kg)
Polysar
DuPont
Butadiene vent shutdown
Chlorinator shutdown
Chlorinator shutdown
Pressure relief
Equipment opening
Accidental releases
Vent
Caustic scrubber relief valve
Equipment opening
Accidental releases
1
4/month
2/month
0
1
0
1
1
0
0
30
30
30
150(68)
24(11)
51(23)
Unknown <150(<68)
360 291(132)
Unknown 40(18)
Source Reference 37.
ABS resins are used to make plastic components for a variety of uses, including
automotive parts, pipe and fittings, appliances, telephones, and business machines. Butadiene
use in resin production accounts for about 5 percent of total butadiene consumption,8
5.5 1
Process Description
ABS resins are synthesized by three polymerization processes: an emulsion
process, a suspension process, and a continuous mass (bulk) process40 The majority of
production is done by batch emulsions. Specialized resins are produced by the
suspension process. These two processes are based on an aqueous-phase reaction. In contrast,
the continuous mass process, the newest technology, does not proceed in water. This eliminates
the need for dewatering and polymer drying, and reduces the volume of wastewater treatment
required.
5-27
-------
TABLE 5-11. ACRYLONITRILE-BUTADIENE-STYRENE RESIN
PRODUCTION FACILITIES
Company
GE
GE'
GE
Dow3
Dow
Dow"
Dowa
Monsanto
Monsanto
Diamond Polymers
Location
Washington, WV
Ottawa, IL
Port Bienville, MS
Midland, MI
Hanging Rock, OH
Allyn's Point, CT
Torrance, CA
Addyston, OH
Muscatine, IA
Akron, OH
Capacity in 1993
tons/yr (Mg/yr)
133,300 (120,000)
173,300(156,000)
101,100(91,000)
71,100(64,000)
45,600(41,000)
30,000 (27,000)
20,000(18,000)
226,700 (204,000)
75,600 (68,000)
8,900 (8,000)
Source: Reference 29.
3 Facility has used polybutadiene as raw material for ABS production since 1985.
Emulsion Process
A block diagram of the ABS emulsion process is shown in Figure 5-641 This
process is referred to as the ABS/styrene-acrylonitrile (ABS/SAN) process because SAN is
prepared in a side step and mixed with graft ABS. Some companies also produce SAN as a
separate product.
The emulsion process involves several steps, from combining the raw materials
with water for aqueous-phase reaction to purification and packaging of the
product resins. Three distinct polymerizations occur in the first few steps: (1) butadiene
polymerizes to form a polybutadiene substrate latex; (2) styrene and acrylonitrile are grafted to
the polybutadiene substrate; and (3) styrene-acrylonitrile copolymer forms.
About 70 to 90 percent of butadiene monomer is converted to polybutadiene in
the first step (Figure 5-6). The unreacted butadiene monomer is removed from the latex in a
5-28
-------
IB '
tb
VO
t
Control
Oevice(e)
(If Installed)
1
r — J-
Butadiene,
Emulalflera,
Initiators,
Wator ^ Butadiene
~ I ( AJ Compreaa
Batch F|
Pressure /\ *• _. .
/ y \ ou
Reactor \/
To Incinerator
or Atmosphere
AN
Absorber
f T
To
Recycle
to
°r l(?)
r ._
f f
•»h » ABS Latex ABS ^ _ ^ c
3per ^3^ " Reactor
StyreneAcrylc
Steam
nNrito. SAN Coagulant
Emulaifiara,
Initiators
AcrylonKrile.
Emu
Itifttr*.
Styrene, ». 8AN Re*ln — __». Coagulal
Catalysts, R"otor <8>
. . f
•^ Centrlfuga .. r)nw»it«rinn
^^^-^^^" ^«nN
,x
Mechanical
Blending
f •
tor —y, -»» Dewaterlng
Packaging
hi DA+K
source: Reference 41 Figure 5-6. Process Diagram for Production of ABS/SAN Via the Emulsion Process
-------
flash stripper (Step 2) and usually recovered. The reactor, stripper, and recovery system vents
are usually directed to a flare or other combustion device. The grafting of acrylonitrile and
styrene to the polybutadiene substrate (Step 3) may be either a batch or continuous process.
Reaction conversion of monomers is 90 to 95 percent. Vapors from the reactors are usually
vented to an acrylonitrile absorber. The absorber is vented to the atmosphere or to an
incinerator.
The ABS plastic is a blend of graft ABS rubber and SAN resin. The blend of
these compounds determines the properties for the ABS product. The copolymer SAN is
prepared in a separate side step. The prepared SAN and graft ABS are mixed at either of two
points in the process. The SAN latex may be blended with graft rubber latex in the coagulator
(Step 4). The agglomerated polymer is dewatered by screening (Step 5), centrifuging (Step 6),
and vacuum filtration (Step 7). No drying step is required. However, some facilities employ a
dryer in place of the centrifuge and vacuum filter.
Alternatively, the SAN latex may be coagulated (Step 8) and dewatered (Step 9)
separately, with the resulting solid resins being mechanically mixed with ABS rubber (Step 10).
In a compounding step, solids are mechanically blended with dyes, antioxidants, and other
additives (Step 10). In the final step (11), the polymer sheets from these operations are
pelletized and packaged.
Suspension Process
A block diagram of the suspension ABS process is shown in Figure 5-7.41 This
process begins with polybutadiene rubber, which is so lightly cross-linked that it is soluble in the
acrylonitrile and styrene monomers. Polybutadiene synthesis is previously described in this
section
Polybutadiene is first dissolved in styrene and acrylonitrile monomers to produce
a solution free of cross-linked rubber gels. A free radical is added to the solution along with
chain-transfer agents in a prepolymerizer (Step 2). After 25 to 35 percent monomer conversion,
5-30
-------
the polymer syrup is transferred to a suspension reactor, where it is dispersed in water with
agitation (Step 3).
After achieving the desired monomer conversion, the products are transferred to a
washing/dewatering system (Step 4), usually a continuous centrifuge. The polymer beads are
then dried in a hot-air dryer (Step 5).
Continuous Mass Process
A block flow diagram for the continuous mass ABS process is shown in Figure 5-8.41 This
process begins with polybutadiene rubber, which is dissolved in styrene and acrylonitrile
monomers (Step 1), along with initiators and modifiers. The ABS polymer is then formed
through phase inversion. Conversion begins in the prepolymerizer (Step 2), where the reaction
causes the ABS rubber to precipitate out of solution. When monomer conversion is about
30 percent complete, the resulting syrup is transferred to the bulk polymerizer, where monomer
conversion is taken to between 50 and 80 percent (Step 3). Unreacted monomer is removed
under vacuum from the polymer melt in the devolatilizer (Step 4). The monomer vapors are
condensed and recycled to the prepolymerizer. The ABS polymer is then extruded, cooled in a
water bath (Step 5), and chopped into pellets (Step 6).
5 5 2 Emissions
As mentioned previously, at least four of the ten facilities producing ABS do not
use butadiene They start instead from polybutadiene and proceed either through the suspension
process or the continuous mass process. Therefore, no butadiene emissions are expected from
these production processes. Of the four remaining plants in operation, data are only available for
three locations and are limited to information on process vents and equipment leaks associated
with the emulsion process. Calculated emission factors are summarized in Table 5-12 as ranges
and are based on data from 1984 appearing in Tables C-19 and C-20 in Appendix C.
5-31
-------
AN Styrene
t/i
LO
to
Polybutediene
Rubber
Initiator*
and
Agitation
Suspending
Agent
Water
Source: Reference 41
Figure 5-7. Process Diagram for Production of ABS via the Suspension Process
(not a source of butadiene emissions)
-------
Initiators & Modifiers
Styrene
Acrylonitrile
U)
*
Source: Reference 41
Figure 5-8. Process Diagram for Production of Bulk ABS
(not a source of butadiene emissions)
-------
The facility emission factor range for process vents includes existing sources, some of which are
controlled. The uncontrolled range represents potential emissions if the sources reported were
not controlled.40
One estimate of emissions from butadiene storage was reported as zero because
butadiene is stored under pressure. Some emissions are possible from secondary sources,
emergency and accidental releases, and transfer and handling raw material losses, but estimates
for these sources are currently unavailable.
Process Vent Emissions
Based on available data, process vent emissions of butadiene occur mainly from
the flash-stripping of the latex from the polymerization reactor in the ABS emulsion process.
The vent emissions from the batch reactors are highly variable, with changing compositions.
Most of these vents are controlled by a flare (control efficiency of 99.9 percent).
Butadiene emissions also occur during the coagulation and dewatering stages and
from intermediate process latex tanks. In 1984, only one facility used a control device. In this
plant, one of the downstream vents was controlled by routing the vent to the plant boiler.
Figure 5-6 shows the process vent locations: Vents A and C through F for emissions directly
associated with the process and Vent B for emissions from a control device.
Equipment Leak Emissions
The estimates for uncontrolled equipment leaks at the two facilities appearing in
Table 5-12 are based on equipment counts provided by the facilities. The CMA estimation
procedure is described in Appendix D. One location reported daily inspection of equipment;
however, no further details on follow-up for any leaks discovered during these inspections were
given. The estimates include some level of control because the average emission rates are based
on practices at butadiene producers.
5-34
-------
TABLE 5-12 SUMMARY OF EMISSION FACTORS FOR ABS PRODUCTION FACILITIES,
EMULSION PROCESS**"
(FACTOR QUALITY RATING E)
Emission Sources
Process Vents
6-41
Secondary Sources
6-41
Facility Emission Factors
Range0 Mean
0.16 - 10.66 Ib/ton (n=3) 4.22 Ib/ton
(0.08 - 5.33 kg/Mg) (2.11 kg/Mg)
NA NA
Uncontrolled Emission
Range c
6.50- 11. 28 Ib/ton (n=3)
(3.25 -5.64 kg/Mg)
NA
Factors
Mean
9.48 Ib/ton
(4.74 kg/Mg)
NA
Source: Reference 40.
Note: Annual emissions from uncontrolled equipment leaks range from 1.21 - 3.50 tons/yr (1.10 - 3.17 Mg/yr) and average 2.36 tons/yr (2.14 Mg/yr) (n=2)." For
£j facilities that reported emissions, none control equipment leaks.
1 Assumes production capacity of 100 percent.
b Factors are expressed as Ib (kg) butadiene emitted per ton (Mg) produced. Data from two facilities are specific to the emulsion process; the third is
assumed to use the same.
c Ranges are based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
n = number of facilities.
NA = not available.
-------
5.6 NITRILE ELASTOMER PRODUCTION
Nitrile elastomer or nitrile-butyl rubber (NBR) is produced by nine facilities.29
The location of the facilities, the type of elastomer produced, and their approximate capacities
are presented in Table 5-13.29
Nitrile elastomer is considered a specialty elastomer and is primarily used for its
oil-, solvent-, and chemical-resistant properties by a variety of manufacturers.42 Some uses
include hose, belting, and cable manufacturing, and molded goods such as seals and gaskets.
Nitrile elastomer production accounts for about 5 percent of total annual butadiene
consumption.8
Several of the facilities involved in NBR production also produce other
elastomers. Goodyear in Texas, Polysar in Tennessee and Texas, Copolymer, and Reichhold all
produce SB copolymers. Because of the common use of butadiene in these production
processes, emissions data often represent total rather than individual process emissions.
Whenever possible, the portion of butadiene emissions directly attributable to nitrile rubber is
shown
5.6 1 Process Description
Nitrile elastomers are copolymers of acrylonitrile and butadiene. They are
produced by emulsion polymerization in batch or continuous processes. The process is
illustrated in the block flow diagram in Figure 5-9.41
The emulsion polymerization process uses water as a carrier medium. Butadiene
and acrylonitrile monomers are piped to agitated polymerization reactors (Step 1) along with
additives and soap. The water not only serves as a reaction medium, but also effectively
transfers the heat of reaction to the cooled reactor surfaces. The additives include a catalyst
5-36
-------
TABLE 5-13. NTTRILE ELASTOMER PRODUCTION FACILITIES
Company
Copolymer
Zeon Chemicals
Goodyear
Polysar Ltd.
BASF
Reichhold Chemicals
Uniroyal Chemical Co.
W. R. Grace
Location
Baton Rouge, LA
Pasadena, TX
Louisville, KY
Houston, TX
Orange, TX
Chattanooga, TN
Cheswold, DE
Painesville, OH
Owensboro, KY
Elastomer Type
Solid rubber
Hydrogenated
Solid rubber
Solid rubber
Solid rubber
Latex
Latex
Solid rubber
Latex
Capacity in 1993 dry
rubber or latex
tons/yr (Mg/yr)
11,100(10,000)
2,200 (2,000)
33,300 (30,000)
34,400(31,000)
2,200 (2,000)
—
—
22,200 (20,000)
Source: Reference 29
"--" means capacity not known.
(cumene hydroperoxide as an oxidizing component), sodium formaldehyde sulfoxylate with
EDTA (ferrous sulfate complexed with ethylenediamine-tetraacetic acid as the reducing
component), and modifiers (alkyl mercaptans).
The reaction is allowed to proceed for 5 to 12 hours. A shortstop solution
(sodium bisulfate or potassium dimethyl dithiocarbonate) is added to terminate the reaction at a
predetermined point, usually after 75 to 90 percent conversion (depending on the desired
molecular weight of the product). The reaction latex is then sent to a blowdown tank (Step 2),
where antioxidants are normally added.
The latex is subjected to several vacuum flash steps (3), where most of the
unreacted butadiene is released. It is then steam-stripped under vacuum (Step 4) to remove the
remaining butadiene and most of the unreacted acrylonitrile. The unreacted monomers are sent
to recovery and recycling. Stripped latex at about 110 to 130°F (43 to 54°C) is pumped to blend
tanks (Step 5).
5-37
-------
Chilled Oil
U)
00
© ©
t ,. 1
AN to y£\ Butad
and Storage Strippar Absorber wj^«nd ^ Absorber or Ree
f <9> ' '
Bottoms \J/
T° St"m Butad
Stripper Separator »•
to stc
Water Butadiene/AN <•>
Butadiene, Butadiene i
Additives Antloxldant 4--
_j ® I £ f" ©
<$. 1 t 4-^, 1
. r I 1 1
Latex
Polymerization ^ Slowdown ^ Vacuum w ^ Blend ^ « . ^
Reactor <2> Tank <*\ Flash <£> /'•""" <5> Tank <<0> Co««ul"U°» ^ "
\/ -s \y Stripper ^ \/ \X
ir ^r
MiMla » »_
Nitnie salts
Latex
N
t
source: Reference 41 Figure 5-9. Process Diagram for Production of Nitrile Elastomer
lene
rage
sycle
lene
rage
?
Screening,
Washing.
Dews to ring
^jf
Drying
i r
Irile Rubber
D Shipping
a.
or
1
-------
Gases released in the flash steps and stripped overhead contain butadiene. These
gases are sent to a partial condenser (not shown) and separator (Step 6), where butadiene vapor
is condensed and sent to liquid storage. Uncondensed butadiene vapor from the separator flows
to an absorber (Step 7), where it is absorbed by countercurrent contact with chilled oil. The
absorber bottoms are pumped to a flash tank (not shown), and dissolved butadiene is released
and returned to the compressor. The hot lean oil is then cooled, chilled, and returned to the top
of the absorber.
Unreacted acrylonitrile in flash vapors and latex stripper overhead is recovered by
sending these gases to a water absorber (Step 8). Absorber bottoms and the liquid phase of the
latex stripper overhead are pumped to a steam stripper (Step 9). The overhead vapor stream
from this stripper is condensed in a decanter. Phase separation is allowed to take place and the
acrylonitrile phase is decanted to storage. The water-rich phase with residual acrylonitrile is
returned to the stripper.
Latex is pumped from the blend tanks (Step 5) to a coagulation tank (Step 10),
where the emulsion is broken by the addition of dilute inorganic salt solution (sodium chloride
or aluminum sulfate) or a weak organic acid. The slurry of fine polymer crumb is then filtered
to remove coagulating chemicals (liquor is recycled) and
may be reslurried for further purification. Crumb is dewatered in an extruder (Step 11), then
hot-air dried (Step 12) Dried rubber is weighed, pressed into bales, and prepared for shipment.
If latex is the desired end product, the final processing steps (coagulation,
screening, washing, and drying) are omitted. The initial steps are essentially identical to those
for solid rubber production.40
5 6.2 Emissions
The availability of emissions data for nitrile elastomer is somewhat limited. At
coproduction facilities, the estimated butadiene emissions include releases from other elastomer
production processes. For the two facilities that are also SB copolymer producers, the percent of
5-39
-------
the total reported emissions assigned to the NBR process was based on the percent of total
production resulting in nitrile elastomer in 1984. Table 5-14 summarizes emissions for process
vents, equipment leaks, and secondary sources. All nitrile elastomer production was assumed to
be operating at full capacity.40 Emissions from emergency and accidental releases and
transfer/handling were not known and storage vent emissions from butadiene storage were
expected to be low because of the use of tanks under pressure.
Process Vent Emissions
All six facilities for which emissions data were reported use some level of
emissions control. Many of the controls that are designed to reduce acrylonitrile emissions are
also effective in reducing butadiene emissions (flares, for example). Data from 1984 for four of
these facilities are summarized as emission factor ranges in Table 5-14 (see Tables C-21 and C-
22 in Appendix C for facility-specific data). The fifth is not used because calculation of an
emission factor might reveal confidential business information on production capacity. Potential
vent locations, shown in Figure 5-9 as Vents A through H, are based on information on the vent
locations supplied by five facilities.
The emission factor ranges were developed as described in Section 4.0. The
facility emission factor range includes the various levels of control that each facility has in place.
Control efficiencies varied from 89 percent to 99.9 percent. The uncontrolled emission factor
range represents potential emissions if controls were not in use.
Equipment Leak Emissions
The estimates for equipment leaks provided by three facilities span three orders of
magnitude (Table 5-14). These estimates include the level of control at butadiene producers
because of how the average emission rates were derived. The only known control devices
currently in use are rupture discs and a flare for pressure relief devices by one facility. The other
three facilities indicate daily visual inspection of equipment; however, no repair programs were
described for any of the leaks found. Although some controls are in place, detailed information
that could be used to compare practices with those at butadiene producers was not available.
5-40
-------
TABLE 5-14. SUMMARY OF EMISSION FACTORS FOR NITRILE ELASTOMER PRODUCTION FACILITIES3'1'
(FACTOR QUALITY RATING E)
Emission Sources
Process Vents
3-01-026
Secondary Sources6
3-01-026
Facility Emission
Range'
0.0004- 17. 80 Ib/ton (n=6)
(0.0001 -8.90kg/Mg)
0.002 -0.01 8 lb/ton(n=2)
(0.001 - 0.009 kg/Mg)
Factors
Mean
~ 4 Ib/ton
(~ 2 kg/Mg)
O.OlOlb/ton
(0.005 kg/Mg)
Uncontrolled Emission Factors
Range Mean
0.030 - <50 Ib/ton (n=6) ~ 16 Ib/ton
(0.01 - <25 kg/Mg) (~ 8 kg/Mg)
0.002 - 0.018 Ib/ton (n=2) 0.010 Ib/ton
(0.001 - 0.009 kg/Mg) (0.005 kg/Mg)
Source: Reference 40.
Note: Annual emissions from uncontrolled equipment leaks range 0.43 - 18 67 tons/yr (0.39 - 16.93 Mg/yr) and average 8.74 tons/yr (7.93 Mg/yr) (n=3).*
" Assumes production capacity of 100 percent
b Factors are expressed as Ib (kg) butadiene emitted per ton (Mg) produced. Only incomplete data on emissions were available, therefore, values
underestimate emissions.
c Ranges are based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
d Upper value used to prevent disclosing confidential operating capacity.
* Lower end of range is for one solid waste stream; upper end includes solid waste, wastewater and contaminated cooling water.
n = number of facilities.
NA = not available.
-------
Secondary Emissions
One emissions estimate of 132 Ib/yr (60 kg/yr) was provided from secondary
sources.40 This estimate includes wastewater, solid waste, and contaminated cooling water. A
second facility also indicated wastewater and solid waste as potential secondary sources.40 The
butadiene content in the wastewater was undetermined; therefore, emissions could not be
estimated. However, the solid waste stream contains 4 ppm butadiene. Based on a generation
rate of 1063 Ib/day (483 kg/day) and assumptions of continuous operation and total
volatilization, the source's emissions potential is approximately 0.02 tons/yr (20 kg/yr).43
5-42
-------
SECTION 6.0
BUTADIENE EMISSIONS FROM MOBILE SOURCES
This section describes estimation methods for butadiene as one component of
mobile source hydrocarbon emissions, based on work by EPA's Office of Mobile Sources
(OMS). Butadiene emissions are formed in engine exhaust by the incomplete combustion of the
fuel. Based on the available data, butadiene emissions appear to increase roughly in proportion
to hydrocarbon emissions. Because hydrocarbon emissions are greater from noncatalyst-
controlled engines than from catalyst-equipped engines, butadiene emissions are expected to be
higher from noncatalyst-controlled engines, such as those in lawnmowers and chainsaws.17
Levels of butadiene in gasoline and diesel fuel are expected to be insignificant
because butadiene tends to readily form a varnish that can be harmful to engines; therefore,
refiners try to minimize the butadiene content. As a result, it was assumed that butadiene is not
present in evaporative, refueling, or resting emissions.17
6 1 ON-ROAD MOBILE SOURCES
Results of work by the OMS on toxic emissions from on-road motor vehicles are
presented in the 1993 reportMotor Vehicle-Related Air Toxics Study (MVATS).17 This report
was prepared in response to Section 202(1)(1) of the 1990 Clean Air Act Amendments which
directs EPA to complete a study of the need for, and feasibility of, controlling emissions of toxic
air pollutants that are unregulated under the Act and are associated with motor vehicles and
motor vehicle fuels. The report presents composite emission factors for several toxic air
pollutants, including butadiene.
6-1
-------
The emission factors presented in the MVATS were developed using currently
available emissions data in a modified version of the EPA's MOBILE4.1 emission model
(designated MOBTOX) to estimate toxic emissions as a fraction of total organic gas (TOG)
emissions. All exhaust mass fractions were calculated on a vehicle by vehicle basis for six
vehicle types: light-duty gasoline vehicles, light-duty gasoline trucks, heavy-duty gasoline
trucks, light-duty diesel vehicles, light-duty diesel trucks and heavy-duty diesel trucks. It was
assumed that light-duty gas and diesel trucks have the same mass fractions as light-duty gas
vehicles and diesel vehicles, respectively. For light duty gas vehicles and trucks, mass fractions
were disaggregated for four different catalytic types for running emissions and two different fuel
systems. Heavy-duty gas vehicles were assumed to have a carbureted fuel system with either no
catalyst or three-way catalyst. These mass fractions were applied to TOG emission factors
developed to calculate in-use toxics emission factors.
A number of important assumptions were made in the development of these in-
use toxic emission factors. They include:
1. Increase in air toxics due to vehicle deterioration with increased mileage is
proportional to increase in TOG.
2. Toxics fractions remain constant with ambient temperature changes.
3. The fractions are adequate to use for the excess hydrocarbons that come
from malfunction and tampering/misfueling.
It should be noted that in specific situations, the EPA Mobile models may over or underestimate
actual emissions.
The butadiene emission factors by vehicle class in grams of butadiene emitted per
mile driven are shown in Table 6-1.44 The QMS also performed multiple runs of the MOBTOX
program to derive a pollutant-specific, composite emission factor that represented all vehicle
classes, based on the percent of total vehicle miles traveled (VMT) attributable to each vehicle
class. Table 6-1 also presents the composite emission factor in pounds (grams) of butadiene
emitted per mile driven.17
6-2
-------
TABLE 6-1 BUTADIENE EMISSION FACTORS FOR 1990
TAKING INTO CONSIDERATION VEHICLE AGING (g/mi)
LDGV LDGT1 LDGT2 LDGT HDGV LDDV LDDT HDDV
MC
Weighted
VMTMix
Exhaust
Areas with 0.017 0.026 0.042 0.029 0.087
noI/M
Areas with 0.013 0.026 0.042 0.029 0.087
basic I/M
0.007 0.011 0.057 0.029 0.024
0.007 0.011 0.057 0.029 0.022
U)
Source: Reference 44
LDGV = Light-Duty Gasoline Vehicle
LDGT1 = Light-Duty Gasoline Truck fpick-ups and vans with gross vehicle weight
of 0 to 6000 lb(0 to 272 kg)]
LDGT2 = Light-Duty Gasoline Truck [pick-ups and vans with gross vehicle weight
of 6001 to 8500 Ib (273 to 3,856 kg)]
LDGT = Light-Duty Gasoline Truck (combined category of LDGT 1 and LDGT2)
HDGV = Heavy-Duty Gasoline Vehicle
LDDV = Light-Duty Diesel Vehicle
LDDT = Light-Duty Diesel Truck
HDDV = Heavy-Duty Diesel Vehicle
MC = Motorcycle
-------
The OMS continues to update the on-road mobile sources model. As of the date
of preparation of this report, MOBILESa was available, but butadiene-specific emission factors
had not been generated. Emissions based on this newer model, however, are estimated to be
about 20 percent higher on average than those from MOBTOX. Due to the higher VOC
emission rates associated with the newer model, the emission rates for 1,3-butadiene may also be
incrementally higher.
Use of methanol in motor vehicles will result in substantial 1,3-butadiene
emission reductions. Projected reductions in butadiene levels of approximately 93 percent were
given in a recent comparison of gasoline and 85-percent methanol (M85) emissions from
flexible fuel and variable fuel vehicles.45 Also, butadiene emissions reductions of 99 percent for
optimized flexible fuel vehicles running on 100-percent methanol (M100) fuel were estimated in
EPA's Methanol Special Report.46 Substantial reductions in butadiene emissions are also
expected with use of ethanol as a clean fuel.47 Finally, butadiene emissions with the use of
compressed natural gas are extremely low.48'49
6.2 OFF-ROAD MOBILE SOURCES
For off-road mobile sources, EPA prepared the 1991 report Non-road Engine
Vehicle Emission Study (NEVES),50 which presents emission factors for 79 equipment types,
ranging from small equipment such as lawnmowers and chain saws, to large agricultural,
industrial, and construction machinery (see Table 6-2). Locomotives, aircraft, and rockets are
not included The equipment types were evaluated based on three engine designs: 2-stroke
gasoline, 4-stroke gasoline, and diesel. Sources for the data include earlier EPA studies and
testing and new information supplied by the engine manufacturers for tailpipe exhaust and
crankcase emission. For test data on new engines, adjustments were made to better represent
emissions from in-use equipment because EPA believes the new engine data do not take into
consideration increase in emissions due to engine deterioration associated with increased
equipment age; therefore, new engine data underestimate in-use emissions.50
6-4
-------
TABLE 6-2. OFF-ROAD EQUIPMENT TYPES AND BUTADIENE EMISSION
FACTORS INCLUDED IN THE NEVES (g/hp-hr)
(FACTOR QUALITY RATING E)
2-Stroke Gasoline
Engines
Equipment type, AMS Code
(2-stroke gas/4-stroke gas/diesel)
Lawn and Garden, 22-60/65/70-004-
025 Trimmers/Edgers/Brush Cutters
010 Lawn Mowers
030 Leaf Blowers/Vacuums
040 Rear Engine Riding Mowers
045 Front Mowers
020 Chain Saws <4 hp
050 Shredders <5 hp
01 5 Tillers <5hp
055 Lawn and Garden Tractors
060 Wood Splitters
035 Snowblowers
065 C nippers/Stump Grinders
070 Commercial Turf Equipment
075 Other Lawn and Garden
Equipment
Airport Service, 22-60/65/70-008-
005 Aircraft Support Equipment
010 Terminal Tractors
Recreational, 22-60/65/70-001-
030 All Terrain Vehicles (ATVs)
040 Mmibikes
010 Off-Road Motorcycles
050 Golf Carts
020 Snowmobiles
060 Specialty Vehicles Carts
Exhaust
6.13"
5.68*
5.88*
N/A
N/A
8.14*
5.68*
5.68*
N/A
N/A
5.68*
N/A
5.68*
5.68*
N/A
0 06W
16.38"
N/A
16.38"
16.38"
2.98*
16.38"
Crank
Case
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
0.0 13W
N/A
N/A
N/A
N/A
N/A
N/A
4-Stroke Gasoline
Engines
Exhaust
0.66*
1.03*
0.53*
0.25*
0.25*
N/A
1. OS-
LOS*
0.26*
1.03*
1.03*
0.74b
0.26*
1.03*
0.1 3b
0.1 3b
2.73"
2.73"
1.95b'e
2.73"
N/A
2.73"
Crank
Case
0.104*
0.162*
0.083*
0.040*
0.040*
N/A
0.162*
0.162*
0.040*
0.162*
0.162*
0.1 62b
0.040*
0.162*
0.029b
0.029b
0.429"
0.429"
0.429b'e
0.429"
N/A
0.429"
Diesel Engines
Exhaust
N/A
N/A
N/A
0.02
N/A
N/A
N/A
N/A
0.02
0.02
N/A
0.02
N/A
0.02
0.03'
0.03C
N/A
N/A
N/A
N/A
N/A
0.02'
Crank
Case
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/AC
N/AC
.
N/A
N/A
N/A
N/A
N/A
N/A°
6-5
-------
TABLE 6-2. CONTINUED
2-Stroke Gasoline
Engines
Equipment type, AMS Code
(2-stroke gas/4-stroke gas/diesel)
Recreational Marine Vessels,
22-82-005/010/020-
005 Vessels w/Inboard Engines
010 Vessels w/Outboard Engines
Vessels w/Stemdrive Engines
020 Sailboat Auxiliary Inboard
Exhaust
11.36W
11.36b-f
11.36W
N/A
Crank
Case
N/A
N/A
N/A
N/A
4-Stroke Gasoline
Engines
Exhaust
1.41W
1.7 lw
1.41W
1.41M
Crank
Case
N/A
0.376W
N/A
N/A
Diesel Engines
Exhaust
0.39f
0.39f
0.39f
1.96f
Crank
Case
N/A
0.008f
N/A
N/A
Engines
025 Sailboat Auxiliary Outboard
Engines
11.36"'
N/A
0.376b'f
1.96f 0.039f
Light Commercial, less than 50 HP,
22-60/65/70-006-
005 Generator Sets
010 Pumps
015 Air Compressors
020 Gas Compressors
025 Welders
030 Pressure Washers
Industrial, 22-60/65/70-003-
010 Aenal Lifts
102 Forklifts
030 Sweepers/Scrubbers
040 Other General Industrial
Equipment
050 Other Material Handling
Equipment
5.68'
0.12"-d
N/A
0.08M
N/A
N/A
0.06M
0.06M
0 06M
4.06b
N/A
0.0 IS"-*
N/A
0.0 18W
N/A
N/A
0.0 19M
0.019b-d
0.0 19M
N/A
0.26*
0.26'
0.26'
N/A
0.26"
0.26"
0.13b
0.13"
0.13"
0.1 3b
0.041"
0.041"
0.041"
N/A
0.041"
0.041"
0.029"
0.029"
0.029"
0.029"
0.02
0.02
0.02
N/A
0.02
0.02
0.03"
0.03C
0.03°
0.03C
N/A
N/A
N/A
N/A
N/A
N/A
N/AC
N/AC
N/AC
N/AC
N/A
N/A
0.13"
0.029"
0.03C
N/AC
Construction, 22-60/65/70-002-
003 Asphalt Pavers
006 Tampers/Rammers
009 Plate Compactors
012 Concrete Pavers
015 Rollers
018 Scrapers
021 Paving Equipment
N/A
5.68"
5.68"
N/A
N/A
N/A
5.68"
N/A
N/A
N/A
N/A
N/A
N/A
N/A
0.1 3b
0.18"
0.18"
N/A
0.25"
N/A
0.18"
0.028"
0.028"
0.028"
N/A
0.040"
N/A
0.028"
0.01
0.00
0.01
0.02
0.01
0.01C
0.02
N/A
0.00
N/A
N/A
N/A
N/AC
N/A
6-6
-------
TABLE 6-2. CONTINUED
2-Stroke Gasoline
Engines
Equipment type, AMS Code
(2-stroke gas/4-stroke gas/diesel)
Construction, 22-60/65/70-002- (con't)
024 Surfacing Equipment
027 Signal Boards
030 Trenchers
033 Bore/Drill Rigs
036 Excavators
039 Concrete/Industrial Saws
042 Cement and Mortar Mixers
045 Cranes
048 Graders
051 Off-Highway Trucks
054 Crushing/Proc. Equipment
057 Rough Terrain Forklifts
060 Rubber Tire Loaders
063 Rubber Tire Dozers
066 Tractors/Loaders/Backhoes
069 Crawler Tractors
072 Skid Steer Loaders
075 Off-Highway Tractors
078 Dumpers/Tenders
08 1 Other Construction Equipment
Agricultural, 22-60/65/70-005-
010 2-Wheel Tractors
0 1 5 Agricultural Tractors
030 Agricultural Mowers
020 Combines
035 Sprayers
025 Balers
040 Ti Hers >5hp
045 Swathers
050 Hydro Power Units
055 Other Agricultural Equipment
Exhaust
N/A
N/A
N/A
5.68'
N/A
N/A
N/A
• • N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
Crank
Case
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
4-Stroke Gasoline
Engines
Exhaust
0.18'
0.18"
0.1 3b
0.13"
0.13"
0.18*
0.1 8a
0.1 3b
N/A
N/A
0.1 3b
0.1 3b
0.1 lb
N/A
0.13"
N/A
0.1 3b
N/A
0.18"
0.1 3b
0.15'
0.11"
0.20"
0.1 4b
0.1 4b
N/A
1.03'
0.1 4b
0.20"
0.1 4b
Crank
Case
0.028'
0.028"
0.028b
0.028"
0.028"
0.028'
0.028'
0.028"
N/A
N/A
0.028"
0.028"
0.024"
N/A
0.028"
N/A
0.028"
N/A
0.028'
0.028"
0.024'
0.024"
0.031'
0.031"
0.031"
N/A
0.162'
0.031"
0.03 r
0.031"
Diesel Engines
Exhaust
0.00
0.02
0.02C
0.02C
o.or
0.02C
0.02
0.02C
0.02C
o.or
0.02C
0.03C
0.01°
o.or
0.02C
0.02C
0.03C
0.04C
o.or
0.02C
N/A
0.04C
N/A
0.02'
0.04
0.04
0.02
0.01
0.04
0.03
Crank
Case
0.00
N/A
N/AC
N/AC
N/AC
N/AC
N/A
N/AC
N/AC
N/AC
N/AC
N/AC
N/AC
N/AC
N/AC
N/AC
o.oo r
o.oo r
N/AC
N/AC
N/A
o.oo r
N/A
N/AC
0.001
0.001
N/A
N/A
0.001
0.001
6-7
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TABLE 6-2. CONTINUED
2-Stroke Gasoline
Engines
Equipment type, AMS Code
(2-stroke gas/4-stroke gas/diesel)
Logging, 22-60/65/70-007-
005 Chain Saws >4 hp
010 Shredders >5 hp
015 Skidders
020 Fellers/Bunchers
Exhaust
4.15'
N/A
N/A
N/A
Crank
Case
N/A
N/A
N/A
N/A
4-Stroke
Gasoline
Engines
Exhaust
N/A
0.25'
N/A
N/A
Crank
Case
N/A
0.040'
N/A
N/A
Diesel Engines
Exhaust
N/A
N/A
o.o r
o.or
Crank
Case
N/A
N/A
N/AC
N/AC
Source: Reference 50.
* Adjusted for in-use effects using small utility engine data.
b Adjusted for rn-use effects using heavy duty engine data.
c Exhaust HC adjusted for transient speed and/or transient load operation.
d Emission factors for 4-stroke propane-fueled equipment.
•g/hr
f g/gallon.
N/A = Not applicable.
Although these emission factors were intended for calculating criteria pollutant
(VOCs, NOX, CO) emissions for SIP emissions inventories, emission factors for several
hazardous air pollutants (HAPs), including butadiene, were derived so that national air toxics
emissions could be estimated. To estimate butadiene emissions, EPA expressed butadiene
emissions as a weight percent of tailpipe exhaust hydrocarbons plus crank case hydrocarbons and
combined the weight percents with existing hydrocarbon emission factors. The weight percents
butadiene applied to all categories of equipment were 1.6 and 1.3 for diesel and gasoline
engines, respectively. These are based on the recommendations from an EPA report Non-road
Emission Factors of Air Toxics*1 that are based on automobile test data. For emissions from
diesel-fueled marine vessels, high-speed, agricultural, construction and large utility equipment,
the report suggests use of weight factors 1.5 percent for direct injection, and 1.7 percent for
indirect injection diesel engines. For emissions from unleaded non-catalyst gasoline-powered
marine vessels, agricultural, construction and large utility equipment, a 1.3 percent weight factor
is recommended.51 The NEVES distinguished between off-road diesel and gasoline engines and
applied the diesel and gasoline weight percents to all equipment types. Future work may provide
equipment-specific values and the use of these should be considered instead.
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The most accurate emission estimate requires that the emission factors be used
with local activity data. If these data are unavailable, a state may elect to approximate emissions
using estimates from the NEVES for 24 nonattainment areas. Taking this approach, the state
chooses one of the 24 nonattainment areas which best represents the state's offroad activity. The
corresponding emission estimate is then adjusted by applying a ratio of the population for the
two areas to more closely approximate the state's emissions. The NEVES report also provides
estimates for counties in the 24 nonattainment areas; therefore, state and local agencies may
prepare regional or county inventories by applying a population ratio to the NEVES estimates.
For further details on the estimation procedure, the reader should refer to the NEVES report.
6.2.1 Marine Vessels
For commercial marine vessels, the NEVES report includes VOC emissions for
six nonattainment areas taken from a 1991 EPA study Commercial Marine Vessel Contribution
to Emission Inventories*2 This study provided hydrocarbon emission factors for ocean-going
commercial vessels and harbor and fishing vessels. The emission factors are shown in
Table 6-3
Ocean-going marine vessels fall into one of two categories—those with steam
propulsion and those with motor propulsion. Furthermore, they emit pollution under two modes
of operation: underway and at dockside (hotelling). Most steamships use boilers rather than
auxiliary diesel engines while hotelling. Currently, there are no butadiene toxic emission
fractions for steamship boiler burner emissions. The emission factors for motor propulsion
systems are based on emission fractions for heavy-duty diesel vehicle engines. For auxiliary
diesel generators, emission factors are available only for 500 KW engines, since the 1991 Booz-
AJlen and Hamilton52 report indicated that almost all generators were rated at 500 KW or more.
For harbor and fishing vessels, butadiene emission factors for diesel engines are
provided for the following horsepower categories - less than 500 hp, 500 to 1,000 hp, 1,000 to
6-9
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1,500 hp, 1,500 to 2,000 hp, and greater than 2,000 hp. In each of these categories, emission
factors are developed for full, cruise, and slow operating modes. Butadiene emission factors are
also provided for gasoline engines in this category. These emission factors are not broken down
by horsepower rating, and are expressed in grams per brake horsepower hour rather than pounds
per thousand gallons of fuel consumed.
6.2.2 Locomotives
As noted in the U.S. EPA's Procedures for Emission Inventory Preparation,
Volume IV: Mobile Sources*3 locomotive activity can be defined as either line haul or yard
activities. Line haul locomotives, which perform line haul operation, generally travel between
distant locations, such as from one city to another. Yard locomotives, which perform yard
operations, are primarily responsible for moving railcars within a particular railway yard.
The OMS has included locomotive emissions in its Motor Vehicle-Related Air
Toxic Study11 The emission factors used for locomotives in this report are derived from the
heavy-duty diesel on-road vehicles as there are no emission factors specifically for locomotives.
To derive toxic emission factors for heavy duty diesel on-road vehicles, hydrocarbon emission
factors were speciated. The emission factors provided in this study (shown in Table 6-4) are
based on fuel consumption.54
6.2.3 Aircraft
There are two main types of aircraft engines in use: turbojet and piston. A
kerosene-like jet fuel is used in the jet engines, whereas aviation gasoline with a lower vapor
pressure than automotive gasoline is used for piston engines. The aircraft fleet in the United
States numbers about 198,000, including civilian and military aircraft.55 Most of the fleet is of
the single- and twin-engine piston type and is used for general aviation. However, most of the
6-10
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TABLE 6-4. BUTADIENE EMISSION FACTORS FOR LOCOMOTIVES
Source Toxic Emission Fraction Emission Factor (Ib/gal)
Line Haul Locomotive 0.0158* 0.00033
Yard Locomotive 0.0158* 0.00080
Source: Reference 54.
1 These fractions are found in Appendix B6 of Reference 55, and represent toxic emission fractions for heavy-duty
diesel vehicles. Toxic fractions for locomotives are assumed to be the same, since no fractions specific for
locomotives are available. It should be noted
fuel is consumed by commercial jets and military aircraft; thus, these types of aircraft contribute
more to combustion emissions than does general aviation. Most commercial jets have two,
three, or four engines. Military aircraft range from single or dual jet engines, as in fighters, to
multi-engine transport aircraft with turbojet or turboprop engines.56
Despite the great diversity of aircraft types and engines, there are considerable
data available to aid in calculating aircraft- and engine-specific hydrocarbon emissions, such as
the database maintained by the Federal Aviation Administration (FAA) Office of Environment
and Energy, FAA Aircraft Engine Emissions Database (FAEED).57 These hydrocarbon emission
factors may be used with weight percent factors of butadiene in hydrocarbon emissions to
estimate butadiene emissions from this source. Butadiene weight percent factors in aircraft
hydrocarbon emissions are listed in the EPA SPECIATE database58 and are presented
inTable 6-5 59
Current guidance from EPA for estimating hydrocarbon emissions from aircraft
appears in Procedures for Emission Inventory Preparation, Volume IV: Mobile Sources™ The
landing/takeoff (LTO) cycle is the basis for calculating aircraft emissions. The operating modes
in an LTO cycle are: (1) approach, (2) taxi/idle in, (3) taxi/idle out, (4) takeoff, and
(5) climbout. Emission rates by engine type and operating mode are given and require that the
fleet be
6-11
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TABLE 6-5. BUTADIENE CONTENT IN AIRCRAFT LANDING AND
TAKEOFF EMISSIONS
SPECIATE
Profile # Description
1097
1098
1099
1214
Military Aircraft
Commercial Aircraft
General Aviation
Pistons
Turbines
Composite of 6 engines
Weight Percent
AMS Code Butadiene
22-75-001-000
22-75-020-000
22-75-050-000
22-75-001-000
1.89
1.80
1.57
0.98
1.57
3.85
Factor
Quality
B
B
C
C
C
C
. burning JP-4 fuel at 75%
power
1215 Composite of 6 engines
burning JP-4 fuel at 30%
power
1216 Composite of 6 engines
burning JP-4 fuel across all
powers
1217 Composite of 6 engines
burning JP-4 fuel at idle
power
1218 Composite - TF-39 engine
burning JP-5 fuel across all
powers
1219 Composite - CTM-56 engine
burning JP-5 fuel across all
powers
1220 Composite - J79 engine
burning JP-4 fuel across all
powers
22-75-001-000
22-75-001-000
22-75-001-000
22-75-001-000
22-75-001-000
22-75-001-000
1.00
2.08
2.20
2.86
2.47
2.01
Source References 58 and 59.
6-12
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characterized and the time in each of the operating modes determined. From this information,
hydrocarbon emissions can be calculated for one LTO for each aircraft type in the fleet. To
determine total hydrocarbon emissions from the fleet, the emissions from a single LTO for the
aircraft type must be multiplied by the number of LTOs for each aircraft type. The weight
percent factor for butadiene can be applied to the total hydrocarbon emissions to estimate the
butadiene emissions.
The emission estimating method noted above is the preferred approach as it takes
into consideration differences between new and old aircraft. If detailed aircraft information is
unavailable, hydrocarbon emission indices for representative fleet mixes are provided in the
emissions inventory guidance document Procedures for Emissions Inventory Preparation,
Volume IV: Mobile Sources60 The hydrocarbon emission indices are 0.394 pounds per LTO
(0.179 kg per LTO) for general aviation and 1.234 pounds per LTO (0.560 kg per LTO) for air
taxis
The butadiene fraction of the hydrocarbon total can be estimated by using the
percent weight factors from SPECIATE. Because air taxis have larger engines and more of the
fleet is equipped with turboprop and turbojet engines than is the general aviation fleet, the
percent weight factor is somewhat different from the general aviation emission factor. To
approximate a butadiene percent weight factor for air taxis, the commercial and general aviation
percent weight factors were averaged (see Table 6-6).58'60'61 6.2.4
Rocket Engines
Butadiene has also been detected from rocket engines tested or used for space
travel. Source testing of booster rocket engines using RP-1 (kerosene) and liquid oxygen have
been completed at an engine test site. Tests for butadiene were taken for eight test runs sampling
four locations within the plume envelope below the test stand. Results from these tests yielded a
range of butadiene emission factors-0.0368 to 0.47 Ibs/ton (0.0151 to 0.193 kg/Mg) of fuel
combusted (factor quality rating C)~providing an average emission factor of 0.14 Ib/ton
6-13
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TABLE 6-6. BUTADIENE EMISSION FACTORS FOR GENERAL AVIATION AND AIR
TAXIS4
Aircraft Type
General
Aviation
Air Taxis
1990 National
LTOsb
19,584,898
4,418,836
Hydrocarbon
Emission
Indices6
0.394 Ib/LTO
1.2341b/LTO
Hydrocarbon
Total in tons
(Mg)
3,858
(3,472)
2,726
(2,454)
Butadiene
Weight
Percentd
1.57
1.69
Butadiene
Emissions in
tons (Mg)
61
(55)
46
(42)
" From Federal Aviation Administration-Controlled Towers.
b Source: Reference 61.
c Source. Reference 60.
d Source: Reference 58.
(0.058 kg/Mg) of fuel combusted. It should be noted that booster fuel consumption is
approximately five times that of sustainer rocket engines.4'62
6-14
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SECTION 7.0
EMISSIONS FROM MISCELLANEOUS SOURCES OF BUTADIENE
This section provides an overview of the miscellaneous sources of butadiene
emissions. These sources can be divided into the following categories: miscellaneous chemical
production; secondary lead smelting; petroleum refining; combustion sources (biomass burning,
scrap tire burning, and stationary internal combustion sources); and "other." With regard to the
chemical production category, the major uses of butadiene were discussed in Section 5.0.
Section 7.0 identifies the smaller consumers, which account for about 8 percent of butadiene use
in the United States. Available details of the production process and associated emissions are
provided, where known. Often these details are incomplete; therefore, readers should contact the
facilities directly for the most accurate information.
The biomass burning and scrap tire burning categories are extremely diverse
sources and are therefore difficult to quantify. This section describes the various types of
burning and any associated emissions. The "other" category contains sources that have been
identified as possible butadiene sources, but for which specific emissions data are lacking.
7 1 MISCELLANEOUS USES OF BUTADIENE IN CHEMICAL PRODUCTION
Eighteen companies at 19 locations are producing 14 different products from
butadiene. Originally identified in a summary report on miscellaneous butadiene uses,35 this list
of facilities has been updated using the 7993 Directory of Chemical Producers - U.S.A. These
facilities are summarized in Table 7-1, along with estimated capacities.19'29 Because data
corresponding to each location are not readily available, all the production process descriptions,
current as of 1984, appear first, followed by a summary of any emissions estimates.
7-1
-------
7.1.1 Product and Process Descriptions
Styrene-Butadiene-Vinylpyridine (SBV) Latex
No information on the production process or the use of styrene-butadiene-
vinylpyridine latex is available. As a copolymer, its production process is likely to be similar to
that of other copolymers.
Tetrahydrophthalic (THP) Anhydride and Acid
Tetrahydrophthalic anhydride and acid (the acid is the hydrate form of the
chemical) may be used either as a curing agent for epoxy resins or as an intermediate in the
manufacture of Captan®, an agricultural fungicide.
In the manufacture of the anhydride as a curing agent, Mobay Synthetics
(formerly Denka) is reported to use the following process. Liquid butadiene is first pressure-fed
to a vaporizer. The resulting vapor is then pressure-fed to the reactor, where reaction with
molten maleic anhydride occurs. Maleic anhydride is consumed over a period of 6 to 10 hours.
The product, molten THP anhydride, is crystallized onto a chill roller at the bagging operation.
Solidified anhydride is cut from the roller by a doctor blade into a weighed container, either a
bag or drum.63 Because ArChem also uses THP anhydride in epoxy resins, use of a process
similar to Mobay Synthetics' was assumed.35
ICI American Holdings, Inc. (formerly Calhio) was reported to generate the
anhydride for captive use as an intermediate for Captan®. In the generation process, butadiene
is charged to reactors along with maleic anhydride to produce THP anhydride. The reaction is a
Diels-Alder reaction, run under moderate temperature and pressure.64
7-2
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TABLE 7- \. MISCELLANEOUS USES OF BUTADIENE IN CHEMICAL PRODUCTION
Capacity in 1993
Company Location Product Mode of Operation tons/yr (Mg/yr)
Ameripol Synpol
ArChem Company
B. F. Goodrich Company
ICI American Holdings,
Inc.
Chevron Chemical
DuPont
DuPont
Dixie Chemical Company
GenCorp
Goodrich
Goodyear
Kaneka Texas
Corporation
Metco America
Port Neches, TX
Houston, TX
Akron, OH
Perry, OH
Richmond, CA
Beaumont, TX
Victoria, TX
Bayport, TX
Mogadore, OH
Akron, OH
Calhoun, GA
Bayport, TX
Axis, AL
Styrene-butadiene-
vinylpyridine (SBV) Latex
Tetrahydrophthalic (THP)
Anhydride
Butadiene-vinylpyridine
Latex
Captan®
Captafol®
1,4-Hexadiene
Dodecanedioic Acid
Butadiene Dimers
THP Anhydride
SBV Latex
SBV Latex
SBV Latex
Methyl Methacrylate-butadiene-
styrene (MBS)
Resins
MBS Resins
Unknown
Batch
Batch
(on demand)
Batch
Continuous
Continuous
Continuous (2 weeks
per month due to low
demand)
Unknown
Unknown
Unknown
Unknown
Unknown
Batch
Unknown
572(515)
25,600 (23,000)
20,000(18,000)
(continued)
-------
TABLE 7-1 CONTINUED
Company
Mobay Synthetics
Corporation"
Phillips Chemical
Company
Rohm and Haas Company
Shell Oil Company
Standard Oil Chemical
Company
Union Carbide
Location
Houston, TX
Borger, TX
Louisville, KY
Norco, LA
Lima, OH
Institute, WV
Product
THP Acid
Butadiene Cylinders b
Butadiene-furfural Cotrimerb
Sulfolane
MBS Resins
Sulfolane
Methyl Methacrylate-
acry 1 onitrile-butadi ene-styrene
(MABS) Polymer
Butadiene Dimers
Ethylidene Norbornene
Mode of Operation
Batch
Batch
Continuous,
intermittent, about
65% of the time
Batch
Batch
Unknown
Unknown
Continuous
Continuous
Capacity in 1993
tons/yr (Mg/yr)
1,700(1,500)
539 (485)
50 (45)
25,500 (23,000)
7,200 (6,500)
Source: References 19 and 29.
" Formerly Denka.
b Process in operation in 1984, status unknown in 1994.
" " means capacity not known
"—" means company-confidential.
-------
Butadiene-Vinylpyridine Latex
Butadiene-vinylpyridine latex is produced at the B. F. Goodrich, Akron, Ohio,
facility as an ingredient in an adhesive promoter. As a copolymer, the production process is
similar to that of other copolymers, usually involving an emulsion polymerization process.65
B. F. Goodrich operates the process in a batch mode, on a schedule that depends on demand.
The finished latex is blended with SB latex and a phenol-formaldehyde mixture to
form a "dip" or an adhesive promoter. Dip is used with fabrics in geared rubber goods
manufacturing. This includes fabric used in tires, hoses, and belting production.66
Methyl Methacrylate-Butadiene-Styrene Terpolymers
Methyl methacrylate-butadiene-styrene (MBS) terpolymers are produced in resin
form by four companies at four locations. This resin is used as an impact modifier in rigid
polyvinyl chloride products for applications in packaging, building, and construction.35
Production of MBS terpolymers is achieved using an emulsion process in which
methyl methacrylate and styrene are grafted onto an SB rubber. The product is a two-phase
polymer.66
Captan®
In Captan® production, tetrahydrophthalic anhydride is passed through an
ammonia scrubber to produce tetrahydrophthalimide (THPI). Molten THPI is coated onto a chill
roller, where it solidifies into a quasi-crystalline state. THPI is then conveyed into a reactor
containing perchloromethyl mercaptan (PMM). Caustic is charged to the reactor, initiating the
reaction that produces Captan®. Captan® is brought to a higher temperature in the heat
7-5
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treatment tank to remove residual PMM, after which the material passes through a vacuum filter
to remove salt and water. The product cake is dried and collected in a baghouse.64
Captafol®
Chevron produces Captafol®, a fungicide, under the trade name Difolatan® at its
Richmond, California, facility. The only information on the process is that production occurs on
a continuous basis and is carried out in a pressurized system vented to an incinerator.35
1,4-Hexadiene
DuPont produces 1,4-hexadiene for use in manufacturing Nordel® synthetic
rubber. Nordel® polymer is used in the manufacture of rubber goods, wire and cable insulation,
automobile bumpers, and as an oil additive.67
In the reactor, butadiene reacts with ethylene to form 1,4-hexadiene. After
reaction, unreacted 1,3-butadiene and ethylene, along with 1,4-hexadiene and by-products, are
flashed from the catalyst and solvent. The maximum temperature in the process is
approximately 250°F (121 °C). The catalyst solution is pumped back to the reactor; vaporized
components are sent to a stripper column. The column separates ethylene and 1,3-butadiene
from the 1,4-hexadiene product and by-products; unreacted components are pumped back to the
reactor The 1,4-hexadiene and by-products are sent to crude product storage before transfer to
refining The 1,4-hexadiene is refined in low-boiler and high-boiler removal columns and
transferred to the Nordel® polymerization process.68
Dodecanedioic Acid
Dodecanedioic acid (DDDA) is produced by DuPont for use as an intermediate in
the production of 1,5,9-cyclodecatriene, a constituent in the manufacture of DuPont's Quiana®
fabric.68 Butadiene can be converted into several different cyclic or open-chain dimers and
trimers, depending upon the reaction conditions and catalysts. Although vinylcyclohexene and
7-6
-------
1,5-cyclooctadiene are the predominant products, 1,2-divinylcycIobutane may be formed under
suitable reaction conditions. Nickel catalysts are often used in the cyclodimerization and
cyclotrimerization of butadiene; however, complexes of iron, copper (I), zeolite, and
compositions also promote cyclodimerization, often giving cyclooctadiene as the principal
product.68
Butadiene Cylinders
Phillips Chemical Company fills cylinders with butadiene monomer at its Borger,
Texas, facility. .A NIOSH survey report on this facility indicates that these cylinders may be
samples of butadiene taken for process quality control.69 The report describes routine quality
control sampling in the tank farm area in which the samples are collected using pressure
cylinders. Operators connect the sample containers to a process line and open valves to fill the
cylinder. Butadiene fills the container and is purged out of the rear of the cylinder before the
valve is closed, resulting in emissions from the cylinder. The sample container is subjected to
vacuum exhaust under a laboratory hood at the conclusion of sampling.35
Butadiene Furfural Cotrimer
Butadiene furfural cotrimer or 2,3,4,5-bis(butadiene)tetrahydrofurfural,
commonly known as R-11, is used as an insect repellant and as a delousing agent for cows in the
dairy industry The concentrations of R-11 in commercial insecticide spray are generally less
than 1 percent69
Production of R-11 at Phillips' Borger, Texas, facility, occurs intermittently
throughout the year; however, when operating, the production process is a continuous operation.
In the process, butadiene reacts with an excess of furfural in a liquid-phase reactor. The reaction
proceeds under moderate conditions of temperature and pressure and consumes 1 mole of
furfural for 2 moles of butadiene. After a period of 4 to 5 hours, the reaction mixture is
transferred to the reactor effluent surge tank. The mixture proceeds to a vertical column that
separates butadiene dimer by distillation. Butadiene dimer, or 4-vinyl-l-cyclohexane, is
7-7
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recovered from the column and later transported to a refinery for reprocessing in crude catalytic
cracking units.69
Furfural is removed from the reaction products by distillation in a similar column
and recycled to the reactor. The last column in the R-l 1 process runs as a batch operation, and
separates R-l 1 from the polymer kettle product. The kettle product is a crystalline solid that is
disposed of in an on-site landfill. R-l 1, which is in the form of a yellow liquid, is transferred to
storage tanks and shipped to customers in drums.69
Sulfolane
Sulfolane is a common trade name for tetrahydrothiophene 1,1-dioxide. It is used
principally as a solvent for extracting aromatic hydrocarbons from mixtures containing straight-
chained hydrocarbons. Sulfolane is produced by first reacting butadiene and sulfur dioxide to
form 3-sulfolene. The 3-sulfolene is then hydrogenated to produce sulfolane. Phillips' Borger,
Texas, facility is assumed to be using a similar process. The Shell facility at Norco, Louisiana,
has a sulfolane production unit downstream of the butadiene recovery process that is included as
part of the butadiene production facility.19
Methyl Methacrylate-Acrylonitrile-Butadiene-Styrene (MABS) Polymers
MABS polymers are produced by Standard Oil Company under the trade name
Barex®. The MABS copolymers are prepared by dissolving or dispersing polybutadiene rubber
in a mixture of methyl methacrylate-acrylonitrile-styrene and butadiene monomer. The graft
copolymerization is carried out by a bulk or a suspension process. The final polymer is two-
phase, with the continuous phase terpolymer of methyl methacrylate, acrylonitrile, and styrene
grafted onto the dispersed polybutadiene phase.66
These polymers are used in the plastics industry in applications requiring a tough,
transparent, highly impact-resistant, and thermally-formable material. Except for their
transparency, the MABS polymers are similar to the opaque ABS plastics. The primary function
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of methyl methacrylate is to match the refractive indices of the two phases, thereby imparting
transparency.66
Butadiene Dimers
Tetrahydrobenzaldehyde (THE A), a butadiene dimer, is produced by Union
Carbide and DuPont (Victoria, Texas). At Union Carbide, butadiene is reacted with acrolein and
cyclohexane to produce THB anhydride in +90-percent yields over a short period of time when
the reaction is carried out at temperatures up to 392°F (200°C).68 The reaction will also take
place at room temperature in the presence of an aluminum-titanium catalyst. A by-product of
the reaction is 4-vinyl-l-cyclohexane.68 At the Union Carbide facility, THB A is recovered and
the unreacted raw materials are recycled to the feed pot. The feed pot, reactor, recovery stills,
and refined product storage tanks are all vented to a flare header.35 In the absence of process
information at the DuPont facility, it is assumed to be using a similar production process.
Ethylidene Norbornene (ENB)
ENB, produced by Union Carbide, is a diene that is used as a third monomer in
the production of ethylene-propylene-dimethacrylates. Ethylene-propylene-dimethacrylate
elastomers are unique in that they are always unsaturated in the side chain pendant to the main or
backbone chain. Therefore, any oxidation or chemical reaction with residual unsaturation has
only a limited effect on the properties of the elastomer.70
7.1.2 Emissions
No emissions data are available for the following products: SBV latex, Captan®,
Captafol®, THP acid, and ethylidene norbomene. For processes where emissions information is
available, it is limited to three sources: process vents, equipment leaks, and secondary
sources.19'35 Butadiene emissions from raw material storage are expected to be negligible
because butadiene is usually stored under pressure. Some emissions resulting from accidental
7-9
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and emergency releases and transfer and handling of raw materials are likely; however, they
have not generally been quantified.
Data are available for process vent emissions from production processes at eight
facilities. At five of these facilities, flares or boilers are used on some vents to control
emissions. At a sixth facility, emissions reduction is achieved by recovery of the vented stream
off the butadiene-furfural cotrimer process, one of the two process vents identified. Because
every facility did not report an emissions estimate for each process vent listed, emissions data
are incomplete.
The emission factors for process vents and secondary sources are summarized in
Table 7-2,19'35'65 with facility-specific data appearing in Tables C-23 through C-25 in
Appendix C. Ranges are provided if more than one data point was available. The facility
emission factors include the control that each facility providing the data has in place. The
uncontrolled emission factors represent potential emissions if controls were not in use.
Because equipment count data were not readily available, no calculations of
equipment leak emissions using average CMA factors were done. Instead, equipment leak
estimates for eight processes at eight facilities were taken from memoranda prepared for EPA in
1986 I9'35 Because information on emissions control through leak detection and repair programs
was incomplete, adjustments to estimated emissions could not be made. The only other controls
in use were double mechanical pump seals and rupture discs on pressure relief devices.
Based on information on secondary sources from eight facilities, emissions
generally appear to be negligible from these sources, despite different end products. One
exception is the butadiene-vinylpyridine process. The facility estimated butadiene emissions
from wastewater volatilization to be approximately 1.3 tons/yr (1.2 Mg/yr).65
Two estimates for emergency vent releases during upsets, startups, and shutdowns
of the 1,4-hexadiene process are 0.2 tons/yr (0.2 Mg/yr) (uncontrolled) off the abatement
collection system for waste liquid and vapors and 47.5 tons/yr (43.1 Mg/yr) from the reactor
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TABLE 7-2 SUMMARY OF EMISSION FACTORS AND ANNUAL EMISSIONSFROM EQUIPMENT LEAKS
FOR MISCELLANEOUS CHEMICALSPRODUCTIONFAGILITIES^
(FACTOR QUALITY RATING U)
Chemical Produced
Butadiene Cylinders
3-01-153
Butadiene Dimers
3-01
Butadiene-furfural
Cotrimers
3-01
Butadiene-viny Ipy ridine
Latex
3-01-026
Dodecanedioic Acid
6-84-350
1 ,4-Hexadiene
3-01
Source
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
(Wastewater)
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
Facility
Emission Factors
43 2 Ib/ton
<0 1 1 tons/yr
NA
0.030 Ib/ton
4 3 tons/yr
0
440 Ib/ton
1.1 tons/yr
0
0.61 tons/yr
NA
5.73 tons/yr
NA
59 3 tons/yr
0
(21.6kg/Mg)
(<0. 1 Mg/yr)
(0.015kg/Mg)
(3.9 Mg/yr)
(220kg/Mg)
(0.5 Mg/yr)
(0.55 Mg/yr)
(5.2 Mg/yr)
(53.8 Mg/yr)
Uncontrolled
Emission Factors
43.2 Ib/ton
<0. 1 1 tons/yr
NA
1.54 Ib/ton
0
440 Ib/ton
0
NA
5.73 tons/yr
NA
67.7 tons/yr
0
(21.6kg/Mg)
(<0.1 Mg/yr)
(0.77 kg/Mg)
(220kg/Mg)
(5.2 Mg/yr)
(6 1.4 Mg/yr)
(Continued)
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TABLE 7-2. Continued
Chemical Produced
Methy Imethacry 1 ate-
butadiene-styrene Resins
6-41
Sulfolane
3-01
Tetrahydrophthalic
Anhydride/Acid
3-01
Source
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
Facility
Emission Factors
1.81b/ton (0.9kg/Mg)
4.0 - 17.4 tons/yr (3.6 - 15.8Mg/yr)c
(n=2)
0 (n=2)
—
1.8 - 14.7 tons/yr (1.6 - 13.3Mg/yr)c
(n=2)
NA
2.4 tons/yr (2.2 Mg/yr)
0 (n=2)
Uncontrolled
Emission Factors
17.2 Ib/ton
17.4 tons/yr (n=2)
0 (n=2)
— -
1.8-1 4.7 tons/yrc
(n=2)
NA
2.4 tons/yr
0 (n=2)
(8.6 kg/Mg)
(15. 8 Mg/yr)
(1.6- 13.3 Mg/yr)c
(2.2 Mg/yr)
Source: References 19, 35, and 65.
* Assumes production capacity of 100 percent.
b Factors are expressed as Ib (kg) butadiene emitted per ton (Mg) produced and tons (Mg) emitted per year.
c Range is based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
NA = not available.
"—" means not calculated because production capacity was not available.
-------
emergency vent. A brine refrigerated condenser on the reactor emergency vent may afford some
emissions reduction, but an efficiency was not indicated.35
7.2 INDIRECT SOURCES OF BUTADIENE
A number of indirect sources of butadiene emissions have been identified. Each
is described briefly below. Where emissions information was available, this is also provided.
Because of EPA's increasing interest in air toxics, emissions information may be available in the
future; therefore, the reader should consider a literature search to identify new sources of
butadiene and locate emissions data.
7.2.1 Vinyl Chloride Monomer and Polyvinyl Chloride Production
In vinyl chloride monomer (VCM) production, butadiene appears as an impurity
in the final product at a maximum level of 6.0 ppm.71 An emission factor developed for overall
production of polyvinyl chloride (PVC) (SCC 6-46-300-01) at a representative PVC plant was
calculated and is given as 4.6 x 10"4 Ib/ton (2.1 x 10"4 g/kg) PVC produced.
7.2 2 Publicly Owned Treatment Works
Some estimates for emissions from wastewater sent to publicly owned treatment
works (POTWs) by SB copolymer producers, considered a secondary source, were made based
on three industry responses to EPA Section 114 requests.72 Using data on the butadiene content
of wastewater sent to a POTW for each of these facilities and air emission models developed by
EPA's Office of Air Quality Planning and Standards (OAQPS) for treatment, storage, and
disposal facilities, estimated emissions for all three facilities are 21 tons/yr (19 Mg/yr). This
approach did not account for volatilization from wastewater during transport to the POTW.
An emission factor developed for butadiene in influent in a representative POTW
was calculated and is given as 1.7 x 103 Ib/ton (771 g/kg) butadiene in influent.4'72
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7.2.3 Secondary Lead Smelting
Although not a significant source, secondary lead smelters are a source of
1,3-butadiene emissions. The secondary lead smelting industry produces elemental and lead
alloys by reclaiming lead mainly from scrap automobile batteries. There are approximately
23 secondary lead smelters in the United States.73
Lead-acid batteries represent about 90 percent of the raw materials at a typical
secondary lead smelter.73 A typical automotive lead-acid battery is made up of lead, sulfuric
acid electrolyte,, plastic separators, and a plastic casing. Older batteries may have a hard rubber
casing instead of plastic. The plastic battery separators and hard rubber casings on older
batteries are the sources of butadiene emissions from secondary lead smelting.
The secondary lead smelting process consists of (1) breaking lead-acid batteries
and separating the lead-bearing materials from the other materials (including plastic and acid
electrolyte); (2) melting lead metal and reducing lead compounds to lead metal in the smelting
furnace (reverberatory, blast, rotary, or electric); and (3) refining and alloying the lead to
customer specifications.73
The vast majority of butadiene emissions come from the smelting furnace
process. Because of the lower exhaust temperature from the charge column, blast furnaces are
substantially greater sources of organic HAP (including butadiene) and related emissions than
are reverberatory or rotary furnaces. From uncontrolled concentrations of butadiene measured
during testing of a blast furnace outlet, an average emission factor of 1.16 Ib/ton, range 0.78 -
1.54 Ib/ton (0.48 kg/Mg, range 0.32 - 0.63 kg/Mg) was developed.73 For the rotary furnace, the
calculated emission factor was 0.13 Ib/ton (0.05 kg/Mg).
On June 23, 1995, EPA promulgated a NESHAP for the secondary lead
production industry. The regulation rquires a reduction of hazardous air pollutant emissions
from blast furnaces which will include butadiene emissions. All the requirements are to be
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implemented by June 1997. Users of this document should review the requirements to
determine what the emission reductions are.
7.2.4 Petroleum Refining
According to 1992 Toxic Release Inventory (TRI) data, petroleum refineries are
the fourth largest emitters of butadiene following the production of organic chemicals, synthetic
rubber, and plastics and resins74 However, besides the TRI figure of 437,590 Ib/yr
(397,000 Mg/yr) of butadiene emitted, no other emissions numbers were located. The Petroleum
Refineries NESHAP was promulgated on August 18, 1995. Information Collection Request
(ICR) questionnaires supporting that work reported that butadiene is released from blowdown
vents, catalyst regeneration process vents, and miscellaneous vents at vacuum distillation,
alkylation, and thermal cracking units.75 However, Clean Air Act Section 114 questionnaires for
that NESHAP did not require the reporting of butadiene emissions. For equipment leaks, EPA
has prepared average emission rates. These are provided in Appendix D along with a description
of equipment leak estimation methods.
Requirements of this NESHAP and the earlier Benzene NESHAP will reduce
butadiene emissions by an estimated 60 percent, assuming reductions are similar to those for
HAPs and VOCs overall. However, the reader is referred to the regulations to evaluate the exact
impact at a particular facility.
7.2.5 Combustion Sources
Butadiene is produced in the combustion of diverse materials such as gasoline,
diesel oil, wood, and tobacco. Therefore, all combustion processes are potential sources of
butadiene. A brief description of biomass burning, tire burning, and stationary internal
combustion sources and their potential butadiene emissions follow.
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Biomass Burning
Fires are known to produce respirable paniculate matter and toxic substances.
Concern has even been voiced regarding the effect of emissions from biomass burning on
climate change.76 Burning wood, leaves, and vegetation can be a source of butadiene emissions.
In this document, the burning of any wood, leaves, and vegetation is categorized as biomass
burning, and includes yard waste burning, land clearing/burning and slash burning, and forest
fires/prescribed burning.77
Part of the complexity of fires as a source of emissions results from the complex
chemical composition of the fuel source. Different woods and vegetation are composed of
varying amounts of cellulose, lignin, and extractives such as tannins, and other polyphenolics,
oils, fats, resins, waxes, and starches.78 General fuel type categories in the National Fire-Danger
Rating (NFDR) System include grasses, brush, timber, and slash (residue that remains on a site
after timber harvesting).78 The flammability of these fuel types depends upon plant species,
moisture content, whether the plant is alive at the time of burning, weather, and seasonal
variations.
Pollutants from the combustion of biomass include carbon monoxide (CO),
nitrogen oxides, sulfur oxides, oxidants, polycyclic organic matter, hydrocarbons, and paniculate
matter The large number of combustion products is due, in part, to the diversity of combustion
processes occurring simultaneously within fire—flaming, smoldering, and glowing combustion.
These processes are distinct combustion processes that involve different chemical reactions that
affect when and what pollutants will be emitted during burning.78
Emission factor models based on field and laboratory data were developed by the
U.S. Forest Service. These models incorporate variables such as fuel type and combustion types
(flaming or smoldering). Because air toxic substances are correlated with the release of other
primary products of incomplete combustion [CO and carbon dioxide (CO;,)], the models
correlate butadiene with CO emissions.78 These emission factor models were used to develop
emission factors for the biomass burning sub-categories described in the following sections.77
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TABLE 7-3. EMISSION FACTORS FOR 1,3-BUTADIENE FOR BURNING OF YARD
WASTE, LAND CLEARING/BURNING, AND SLASH BURNING
(FACTOR QUALITY RATING U)
Yard Waste Land Clearing/Burning Slash (pile) Burning
(AMS 26-10-030-000) (AMS 28-01-500-000) (AMS 28-10-005-000)
' 0.401b/ton
(0.198g/kfi)
0.32 Ib/ton
(0.163g/kg)
0.32 Ib/ton
(0.163 g/kg)
Source: References 77 and 78.
Because of the potential variety in the fuel source and the limited availability of
emission factors to match all possible fuel sources, emission estimates may not necessarily
represent the combustion practices occurring at every location in the United States. Therefore,
localized practices of such parameters as type of wood being burned and control strategies
should be carefully compared.77
Yard Waste Burning-Yard waste burning is the open burning of such materials
as landscape refuse, wood refuse, and leaves in urban, suburban, and residential areas.77 Yard
waste is often burned in open drums, piles, or baskets located in yards or fields. Ground-level
open burning emissions are affected by many variables, including wind, ambient temperature,
composition and moisture content of the material burned, and compactness of the pile. It should
be noted that this type of outdoor burning has been banned in certain areas of the United States,
thereby reducing emissions from this subcategory.77'79 An emission factor for yard waste is
shown in Table 7-3.77'78
Land Clearing and Slash Burning—This subcategory includes the burning of
organic refuse (field crops, wood, and leaves) in fields (agricultural burning) and wooded areas
(slash burning) in order to clear the land. Burning as part of commercial land clearing often
requires a permit.77 Emissions from organic agricultural refuse burning are dependent primarily
on the moisture content of the refuse and, in the case of field crops, on whether the refuse is
burned in a headfire or a backfire.79 Other variables, such as fuel loading (how much refuse
7-17
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material is burned per unit of land area) and how the refuse is arranged (in piles, rows, or spread
out), are also important in certain instances. Emission factors for land clearing/burning and
slash burning are shown in Table 7-3.77'78
Forest Fires/Prescribed Burning—A forest fire (or wildfire) is a large-scale natural
combustion process that consumes various ages, sizes, and types of outdoor vegetation.80 The
size, intensity, and even occurrence of a forest fire depend on such variables as meteorological
conditions, the species and moisture content of vegetation involved, and the weight of
consumable fuel per acre (fuel loading).80
Prescribed or broadcast burning is the intentional burning of forest acres as part
of forest management practices to achieve specific wildland management objectives. Controlled
burning can be used to reduce fire hazard, encourage wildlife habitat, control insects, and
enhance the vigor of the ecosystem.78 Prescribed burning occurs thousands of times annually in
the United States, and individual fires vary in size from a fraction of an acre to several thousand
acres. Prescribed fire use is often seasonal, which can greatly affect the quantity of emissions
produced.78
HAP emission factors for forest fires and prescribed burning were developed
using the same basic approach as for yard waste and land clearing burning, with an additional
step to further classify fuel types into woody fuels (branches, logs, stumps, and limbs), live
vegetation, and duff (layers of partially decomposed organic matter).77 In addition to the fuel
type, the methodology was altered to account for different phases of burning, namely, flaming
and smoldering.77 The resulting emission factors are shown in Table 7-4.77'78
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TABLE 7-4. EMISSION FACTORS FOR 1,3-BUTADIENE FOR FOREST FIRES AND
PRESCRIBED BURNING BY FUEL TYPE
(FACTOR QUALITY RATING U)
' Fuel Type
Forest Fires
(AMS 28-10-001-000)
Ib/ton (g/kg)
Prescribed Burning (Broadcast)
(AMS 28-10-015-000)
Ib/ton (g/kg)
Fine wood
Small wood
Large wood (flaming)
Large wood (smoldering)
Live vegetation
Duff (flaming)
Duff (smoldering)
0.24(0.12)
0.24(0.12)
0.24(0.12)
0.90 (0.45)
0.52 (0.26)
0.24(0.12)
0.90 (0.45)
0.24(0.12)
0.24(0.12)
0.24(0.12)
0.90 (0.45)
0.52 (0.26)
0.24(0.12)
0.90 (0.45)
Source References 77 and 78.
Tire Burning
Approximately 240 million vehicle tires are discarded annually.81 Although
viable methods for recycling exist, less than 25 percent of discarded tires are recycled; the
remaining 175 million are discarded in landfills, stockpiles, or illegal dumps.81 Although it is
illegal in many states to dispose of tires using open burning, fires often occur at tire stockpiles
and through illegal burning activities.79 These fires generate a huge amount of heat and are
difficult to extinguish (some tire fires continue for months). Butadiene is a major constituent of
the tire fabrication process and is, therefore, present in emissions from tire burning.
Table 7-5 contains emission factors for chunk tires and shredded tires.79'81 When
estimating emissions from an accidental tire fire, it should be kept in mind that emissions from
burning tires are generally dependent on the burn rate of the tire. A greater potential for
emissions exists at lower burn rates, such as when a tire is smoldering rather than burning out of
control.79 The fact that the shredded tires have a lower burn rate indicates that the gaps between
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TABLE 7-5. EMISSION FACTORS FOR 1,3-BUTADBENE FROM
OPEN BURNING OF TIRES (SCC 5-03-002-03)1'b
(FACTOR QUALITY RATING C)
Chunk Tires Shredded Tires
234.28 lb/1000 tons 277.95 lb/1000 tons
(117.14mg/kg) . (138.97 mg/kg)
Source: References 79 and 81.
* Values are weighted averages because of differing bum rates.
b Emissions determined using system response to toluene. Data averaged over six sets of VOST tubes per
day taken over 2 days.
tire materials provide the major avenue of oxygen transport. Oxygen transport appears to be a
major, if not the controlling mechanism for sustaining the combustion process.81
Besides accidental or illegal open burning of tires, waste tires are incinerated for
energy recovery and disposal purposes. Tires are combusted at tire-to-energy facilities, cement
kilns, tire manufacturing facilities, and as supplemental fuel in boilers, especially in the pulp and
paper industry. No emission factors for butadiene from tire incineration have been located.
Other Stationary Combustion Sources
Because butadiene has been detected from mobile combustion sources and
biomass and tire burning, stationary external and internal combustion sources are potential
sources as well. External combustion sources include utility boilers and
residential wood combustion. No emission factors were identified for these sources. Internal
combustion sources include gasoline and diesel engines used for industrial and commercial
activities, as well as gas turbines applied in electric power generation. Available emissions
information is summarized below.
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Gasoline and diesel internal combustion engines are used in aerial lifts, fork lifts,
mobile refrigeration units, generators, pumps, industrial sweepers/scrubbers, and material
handling equipment (such as conveyors). The rated power of these engines covers a substantial
range, up to 250 hp (186 kW) for gasoline engines and up to 600 hp (445 kW) for diesel engines.
These have been included in the off-road sources in Section 6.0. Diesel engines larger than
600 hp (445 kW) are used primarily in oil and gas exploration and production, supplying
mechanical power to operate drilling, mud pumping, and hoisting equipment generators. These
larger diesel engines are frequently used for electrical generation, irrigation, and nuclear power
plant emergency cooling water pump operations.82
Even though butadiene emissions have been quantified for both gasoline and
diesel mobile combustion engines, butadiene emission factors for stationary internal combustion
engines have only been developed for uncontrolled diesel engines (SCCs 2-02-001-02 and
2-03-001-01, industrial and commercial/institutional reciprocating 1C engines, respectively,
fueled with either distillate oil or diesel). The current emission factor provided in the fifth
edition of AP-42 is <0.0000391 Ibs/MMBtu of fuel (<0.017 ng/J of fuel). This emission factor
is rated E due to a limited data set (one diesel engine), and/or a lack of documentation of test
results. Such an emission factor may not be suitable for estimating emissions from specific
facilities and should be used with care.82
Gas turbines greater than 3 MW are primarily used in electrical generation for
continuous, peaking, or standby power. They are also used as gas pipeline pumps, compressor
drivers, and in various process industries. This diversity of uses has lead to the development of a
diversity of engine designs and models using a wide range of fuels, including natural gas,
distillate (No. 2) fuel oil, and in a few cases, residual fuel oil. Although butadiene emissions
from gas turbines are presently being investigated, there are currently no emission factors to
quantify butadiene emissions.82
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7.3 OTHER BUTADIENE SOURCES
Other potential sources of butadiene emissions have been identified by OAQPS,
which has collected information to assist State and local agencies in their toxic air pollutant
programs. The Crosswalk/Air Toxic Emission Factor (XATEF) database83 provides a list of
possible sources for a number of toxic air pollutants. The Standard Industrial Classification
(SIC) Codes identified in the report as possible butadiene sources are shown in Table 7-6.
Data collected by NIOSH during the 1972-1974 National Occupational Health
(NOH) survey84'85 identify additional potential emission sources, which are also listed in
Table 7-6. This work was designed specifically to estimate the number of workers (grouped by
SIC Code) potentially exposed to butadiene. In some cases, the "potential exposure"
determination was supported by observing butadiene in use. However, many of these cases were
based on trade name product use; that is, the product used was derived from butadiene or may
otherwise have a potential to contain butadiene.84 In a 1981-1983 NOH survey, six additional
industries were identified as posing a potential for worker exposure. These industries are also
included in Table 7-6.
It is important to remember that these data were collected by NIOSH to assess
worker exposure. They do not necessarily translate directly into atmospheric emission sources
because of possible in-plant controls and butadiene removal as a result of its reactivity.
However, the list represents several possible sources that may not otherwise be immediately
identified as having a butadiene emissions potential.
Another reference for butadiene sources was the 1992 Toxic Chemical Release
Inventory Data Base,74 in which industry reporting of butadiene releases for 1993 were identified
by SIC Code and are included in Table 7-6.
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TABLE 7-6. POTENTIAL SOURCE CATEGORIES OF BUTADIENE EMISSIONS
1990 SIC Code
1990 Description
2269'
2273b (2272°)
262 ld
2631°
2652b
2812d
2819d
282 ld
2822d
2851b
2865"
2869d
2879d
2899d
2911d
295 lb
"H)92d
30521" (3041)
3(ih1)'" (3031 )
30X", 34.32''
(3079)
3357"
34941'
3499be
353.3b
3569"
3585b
362 lb
3643b
365 lb
Dyeing and finishing of textiles (except wool fabrics and unit-finishers of textiles) not elsewhere
classified
Carpets and rugs
Paper and allied products - paper mills
Paperboard mills
Paperboard containers and boxes - set up paperboard boxes
Industrial inorganic chemicals - alkalis and chlorine
Industrial inorganic chemicals not elsewhere classified
Plastics materials and resins
Synthetic rubber
Paints and allied products
Cyclic crudes and intermediates
Industrial organic chemicals not elsewhere classified
Pesticides and agricultural chemicals not elsewhere classified
Chemicals and chemical preparations not elsewhere classified
Petroleum refining
Asphalt paving and roofing materials - paving mixtures and blocks
Miscellaneous products of petroleum and coal - lubricating oils and greases
Rubber and miscellaneous plastics products - tires and inner tubes
Rubber and plastics footwear
Rubber and plastics hose and belting
Fabricated rubber products not elsewhere classified
Miscellaneous plastics products, plumbing fixtures fitting and trim
Nonferrous wire drawing and insulating
Miscellaneous fabricated metal products - valves and pipe fittings not elsewhere classified
Fabricated metal products not elsewhere classified
Construction, mining, and material handling machinery and equipment - oil and gas field
machinery
General industry machinery and equipment not elsewhere classified
Air-conditioning and warm air heating equipment and commercial and industrial refrigeration
equipment
Electrical industrial apparatus - motors and generators
Electric lighting and wiring equipment - current-carrying wiring devices
Household audio and video equipment
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TABLE 7-6. CONTINUED
1990 SIC Code 1990 Description
3721" Aircraft and parts - aircraft
3799b Transportation equipment not elsewhere classified
3841b Surgical and medical instruments
3996b Linoleum, asphalted felt-base, and other hard surface floor coverings not elsewhere classified
4226* Special warehousing and storage, not elsewhere classified
5014C Motor vehicles and motor vehicle parts and supplies - tires and tubes
5162b, 5169b Chemicals and allied products - plastic materials and (5161") basic forms and shapes not
elsewhere classified
5171b Petroleum and petroleum products - petroleum bulk stations and terminals
5541b Gasoline service stations
6513b Real estate operators - apartment buildings
7319b Advertising not elsewhere classified
7538° Automotive repair shops - general
806b Hospitals
8372, 8741- Commercial economic, sociological, and educational research, management, and public relations
8743b, 8748b services except facilities support
(7392)
873 ld (739D Research, development and testing services - commercial physical and biological research
" SIC Code is listed as a potential source in the EPA XATEF document, Reference 83.
b This source is from the N1OSH NOH 1972-1974 survey, Reference 85. This is the current SIC Code for
this category, the code in parentheses was the code for the category at the time of the survey.
L SIC Code was identified as possible butadiene source during the NIOSH NOH 1981-1983 survey,
Reference 85
d SIC Code was identified from the Toxic Release Chemical Inventory Database for 1993 submittals by
industry', Reference 74
e SIC Code is listed bv both EPA and NIOSH.
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SECTION 8.0
SOURCE TEST PROCEDURES
1,3-Butadiene emissions can be measured by a number of methods. The
following methods are applicable for measuring emissions from stationary sources, ambient air,
and vehicle exhaust: (1) EPA Reference Method 18;86 (2) NIOSH Analytical Method 1024;87
(3) EPA Exhaust Gas Sampling System, Federal Test Procedure (FTP);88 and (4) Auto/Oil Air
Quality Improvement Research Program (AQTRP) speciation methodology.89
EPA Reference Method 18 applies to the sampling and analysis of approximately
90 percent of the total gaseous organics emitted from an industrial source, whereas NIOSH
Method 1024 applies specifically to the collection and analysis of 1,3-butadiene from ambient
air The FTP and AQTRP methods measure vehicle exhaust by bag sampling and gas
chromatography/flame ionization detector (GC/FDD) analysis. All four methods are described in
the following sections.
8 1 EPA REFERENCE METHOD 18
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 8-1. The Tedlar® bag has been used for some
time in the sampling and analysis of source emissions for pollutants. The cost of the Tedlar®
bag is relatively low, and analysis by GC is easier than with a stainless steel cylinder sampler,
because pressurization is not required to extract the air sample in the gas chromatographic
analysis process.90 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,
8-1
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Vsnt
Filter
(glass wool)
Mala Quick
Connectors
Probe
Tenor*
Sample Line
Reverse j
(3") Type
Pitot Tube
00
K)
Stack Wall
Rigid Leakproof Container
i
Source: Reference 86
Figure 8-1. Integrated Bag Sampling Train
-------
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 FDD. Based on field and
laboratory validation studies, the recommended time limit for analysis is within 30 days of
sample collection.91 One recommended column is the 6-ft (1.82-m) Supelco Porapak QS.92
However, the GC operator should select the column and GC conditions that provide good
resolution and minimum analysis time for 1,3-butadiene. Zero helium or nitrogen should be
used as the carrier gas at a flow rate that optimizes the resolution.
The peak areas corresponding to the retention times of 1,3-butadiene are
measured and compared to peak areas for a set of standard gas mixtures to determine the 1,3-
butadiene concentrations. The detection limit of this method ranges from about 1 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 an inert gas or by using smaller gas sampling
loops.
Recent work by EPA's Atmospheric Research and Exposure Assessment
Laboratory has produced a modified version of Method 18 for stationary source sampling.90'93
One difference is in the sampling rate, which is reduced to allow collection of more manageable
gas volumes By reducing the gas volumes, smaller Tedlar® bags (5 to 7L) can be used instead
of the traditional 25-L or larger bags, which are not very practical in the field, especially when a
large number of samples is required.90 A second difference is the introduction of a filtering
medium to remove entrained liquids, which improves the butadiene quantitation precision.
Two other changes involve the analytical procedure. The first uses picric acid in
a second column (2 m x 1/8" stainless steel column, 0.19 percent picric acid on 80/100 mesh
Carbopak C) to minimize the interference by butane and butene isomers that are also present in
the stream. The second uses a backflush-to-vent configuration to remove any high-boiling
compounds that have been collected before they reach the picric acid column. These
8-3
-------
modifications allow more accurate quantitation of butadiene to be performed in a shorter time
period than with Method 18.
8.2 NIOSH METHOD 1024
NIOSH Method 1024 is appropriate for measuring ambient emissions of
1,3-butadiene in the workplace. In this NIOSH method, samples are collected with adsorbent
tubes containing charcoal that has been washed and coated with 10 percent by weight 4-tert-
butylcatechol (TBC-charcoal), a chemical known to inhibit the polymerization of 1,3-butadiene.
Three-liter air samples should be collected with the use of a personal sampling pump at a flow
rate of 0.05 L/min.87'94
Samples are desorbed with carbon disulfide and analyzed by GC equipped with
an FID and a column capable of resolving 1,3-butadiene from the solvent front and other
interferences. The column specified in NIOSH Method 1024 is a 50-m x 32-mm internal
diameter, fused-silica, porous-layer, open-tubular column coated with aluminum oxide and
potassium chloride (A12O3/KC1).87 Degradation of compound separation may be eliminated by
using a back flushable precolumn [e.g., 10-m x 0.5-mm interior diameter fused-silica (CP
Wax 57 CB)]. The precolumn allows light hydrocarbons to pass through, but water, methylene
chloride, and polar or high-boiling components are retained and can be backflushed.87'93
The amount of 1,3-butadiene in a sample is obtained from the calibration curve in
units of micrograms per sample. Collected samples are sufficiently stable to permit 6 days of
ambient sample storage before analysis. If samples are refrigerated, they are stable for 18 days.
Butadiene can dimerize during handling and storage. The rate of dimerization is a function of
temperature, increasing with increasing temperature. Consequently, samples should be stored at
low temperatures.
This procedure is applicable for monitoring 1,3-butadiene air concentrations
ranging from 0.16 ppm to 36 ppm, and is more sensitive and selective than the previously-used
8-4
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NIOSH Method S-91.95 The GC column and operating conditions should provide good
resolution and minimum analysis time.
8.3 FEDERAL TEST PROCEDURE
The most widely-used test procedure for sampling emissions from vehicle exhaust
is the FTP, which was initially developed in 1974.88'96-97 The FTP uses the Urban Dynamometer
Driving Schedule (UDDS), which is 1,372 seconds in duration. An automobile is placed on a
chassis dynamometer where it is run according to the following schedule. 505 seconds of a
cold-start; 867 seconds of hot transient; and 505 seconds of a hot-start. (The definitions of the
above terms can be found in the FTP description in the 40 CFR, Section 86).*8 The vehicle
exhaust is collected in Tedlar® bags during the three testing stages. It should be noted that, in
most cases, the majority of 1,3-butadiene is generated in bag one, the first 505-second segment
of the cold-start UDDS cycle.98
The most widely used method for transporting the vehicle exhaust from the
vehicle to the bags is a dilution tube sampling arrangement identical to the system used for
measuring criteria pollutants from mobile sources.88'98 Dilution techniques are used for sampling
auto exhaust because in theory, dilution helps simulate the conditions under which exhaust gases
condense and react in the atmosphere. Figure 8-2 shows a diagram of a vehicle exhaust
sampling system " Vehicle exhausts are introduced at an orifice where the gases are cooled and
mixed with a supply of filtered dilution air. The diluted exhaust stream flows at a measured
velocity through the dilution tube and is sampled isokinetically.
The major advantage in using a dilution tube approach is that exhaust gases are
allowed to react and condense onto particle surfaces prior to sample collection, providing a truer
composition of exhaust emissions as they occur in the atmosphere. Another advantage is that the
dilution tube configuration allows simultaneous monitoring of hydrocarbons, carbon monoxide,
carbon dioxide, and nitrogen oxides. Back-up sampling techniques, such as filtration/adsorption,
are generally recommended for collection of both paniculate- and gas-phase emissions.97
8-5
-------
Amblwit AH Intol
00
O\
To
Dilution Air
--C
V»htol* x
Exhwtt
InM V
Fb» Control Vilve
EE3 P.rtteuUt. F*er
Pump
T | Twnparalura
S>nior
To
Exhaust Simple Big
-»• To Mrihmol Simple CohoHon
~^Te Form«ld»hrd« Simpto Ce»«otton
PocMf* ObplMOTicnt Pump
Mmonrttr
Oluhtrgi
Source1 Reference 99
Figure 8-2. Vehicle Exhangt Gai Sampling System
-------
8.4AUTO/OIL AIR QUALITY IMPROVEMENT RESEARCH PROGRAM SPECIATION
METHOD
Although there is no EPA-recommended analytical method for measuring
1,3-butadiene from vehicle exhaust, the AQIRP method for the speciation of hydrocarbons and
oxygenates is widely used.89'97 This analytical method calls for a dual column GC with FDD. A
pre-column, 15-m x 0.53-mm interior diameter, 1 jam film, such as the DB-WAX (J & W
Scientific Co, Folsom, CA), is recommended to retain water and alcohols while allowing the
lower molecular weight hydrocarbons to pass rapidly through to the analytical column.89 A
backflush valve can be activated to prevent the polar species and higher hydrocarbons from
entering the analytical column, and to backflush these species from the pre-column. The
recommended analytical column is a 50-m x 0.53-mm interior diameter, 10 urn film, porous
layer open tubular (PLOT) column of alumina deactivated by potassium chloride.89
The peak areas corresponding to the retention times of 1,3-butadiene are
measured and compared to peak areas for a set of standard gas mixtures to determine the
1,3-butadiene concentrations. The detection limit for this method is on the order of 0.03 ppmC
in dilute exhaust for 1,3-butadiene (0.5 mg/mile for the FTP).98
It should be noted that sample instability has been shown to be a problem for
1,3-butadiene in exhaust mixtures. Therefore, to minimize concerns about sample integrity,
exhaust emissions should be analyzed promptly (within 1 hour of collection).98'100
8-7
-------
SECTION 9.0
REFERENCES
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-------
13. Chemical Profile: Neoprene. Chemical Marketing Reporter. 233(19):37, May 1988.
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20. Haddeland, G.E. Butadiene. Process Economics Program, Report No. 35. Menlo
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22 U. S. EP A. Evaluation of PCS Destruction Efficiency in an Industrial Boiler.
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23 U S EPA Efficiency of Industrial Flares: Test Results. EPA-600/2-84-095. Research
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24 U.S EPA. Control Technologies for Hazardous Air Pollutants. EPA/625/6-91/014.
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9-2
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U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards,
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27. Wassel R.A. and K.Q. Kuhn (Radian Corporation). Memorandum to the Butadiene Source
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28. Shreve's Chemical Process Industries. New York, New York: McGraw-Hill, 1984.
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1,3-Butadiene Emissions from Neoprene Facilities and Emissions Reductions Achievable
9-3
-------
with Additional Controls," December 23, 1985.
40. Burt, R. and R. Howie (Radian Corporation). Memorandum to L.B. Evans
(U.S. Environmental Protection Agency, Chemicals and Petroleum Branch) concerning
"Estimates of Acrylonitrile, Butadiene, and other VOC Emissions and Controls for ABS
and NBR Facilities," January 29, 1986.
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Fuel. Special Report. Ann Arbor, Michigan: U.S. Environmental Protection Agency,
Office of Mobile Sources, September 1989.
47 US EPA. Analysis of Economic and Environmental Effects of Ethanol as an Automotive
Fuel. Special Report: Ann Arbor, Michigan: U.S. Environmental Protection Agency,
Office of Mobile Sources, April 1990.
48. California Air Resources Board. Definition of a Low-Emission Motor Vehicle in
Compliance with the Mandates of Health and Safety Code Section 3903 7.05. Assembly
Bill 234, Leonard, 1987. El Monte, California: California Air Resources Board, Mobile
Source Division, 1989.
49. California Air Resources Board. Proposed Reactivity Adjustment Factors for Transitional
Low-Emission Vehicles: Technical Support Document, Updated Version. El Monte,
California: California Air Resources Board, Mobile Source Division, November 13, 1991.
50. U.S. EPA. Non-Road Engine and Vehicle Emission Study. 21A-2001. Washington, D.C.:
U.S. Environmental Protection Agency, Office of Air and Radiation, 1991. pp. 13, 14, 27,
28,31,32,35,36,39,40,138.
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51. Ingalls, M.N. Non-road Emission Factors of Air Toxics. Interim Report No. 2. SWRI08-
3426-005. Ann Arbor, Michigan: U.S. Environmental Protection Agency, June 1991.
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52. Booz-Allen and Hamilton. Commercial Marine Vessel Contribution to Emission
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Motor Vehicle Emission Laboratory, October 7, 1991. Sections 1.0 and 2.0.
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Mobile Sources. Section 6.0 - Emissions for Locomotives. EPA-450/4-81-026d
(Revised). Ann Arbor, Michigan: U.S. Environmental Protection Agency, Office of
Mobile Sources, 1992.
54. U.S. EPA. Motor Vehicle-Related Air Toxic Study. EPA-420/R-93-005. Ann Arbor,
Michigan: U.S. Environmental Protection Agency, Office of Mobile Sources, April 1993.
55. U.S. Department of Transportation. Census of U.S. Civil Aircraft. Washington, D.C.:
U.S. Department of Transportation, Federal Aviation Administration, Office of
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Quality Planning and Standards, July 1993. pp. 1-6.
57. U.S. Department of Transportation. Federal Aviation Engine Emission Database.
Washington, D.C.: U.S. Department of Transportation, Office of Environment and
Energy, Federal Aviation Administration, 1991.
58 U. S. EP A. Volatile Organic Compound/f 'articulate Matter Speciation Data System
(SPEC1ATE). Version 1.5. Research Triangle Park, North Carolina: U.S. Environmental
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59 Vigyan Inc Estimation and Evaluation of Cancer Risks Attributed to Air Pollution in
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April 1993.
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Ann Arbor, Michigan: U.S. Environmental Protection Agency, Office of Mobile Sources,
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1988), B. F. Goodrich. Telephone communications.
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68 Kirschenbaum, I. Diels-Alder Reactions. In: Encyclopedia of Chemical Technology,
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69 U.S. Department of Health and Human Services. Industrial Hygiene Survey Report of
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70 Bisio, A.L. and B.R. Tegge. Ethanol - Propylene Elastomers In: Encyclopedia of
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71 Khan, Z.S., and T.W. Hughes (Monsanto Research Corporation). Source Assessment:
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72. White, T.S. (Radian Corporation). Volatile Organic Compound Emissions from Rubber
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74. U.S. EPA. 1992 Toxic Chemical Release Inventory (SARA 313) Database. Washington,
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Analysis," August 25, 1993.
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Preliminary Estimates. Presented at the 85th Annual Meeting and Exhibition of the Air
and Waste Management Association, June 1992. pp. 2-13.
77. Campbell, D.L. and J. Mangino (Radian Corporation). Evaluation and Improvement of the
Puget Sound Toxic Air Contaminants Emissions Inventory. Technical Note. EPA
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Office of Research and Development, May 1994.
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from Prescribed Fires in the United States for 1989. U.S. Department of Agriculture,
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Stationary Point and Area Sources. Section 2.4. Research Triangle Park, North Carolina:
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80 AP-42, 5th ed., op. cit., note 79. Section 11.1, 1995.
81 Lemieux, P.M., and D.M. DeMarini. Mutagenicity of Emissions from the Simulated Open
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82 AP-42, 5th ed., op. cit., note 79. Section 3.3, 1995.
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Ohio). Telephone communication, July 26, 1988.
85. "National Occupational Hazard Surveys, extracted data from 1972-1974 and 1981-1983,"
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Section, Cincinnati, Ohio. July 1987.
86. Federal Register. 48 FR 48344-46361, October 18, 1983.
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88. U.S. Code of Federal Regulations, Title 40, Protection of the Environment, Part 86,
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Emissions Monitoring Systems Laboratory). Written communication, June 6, 1988.
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1,3-Butadiene. 1987. pp. 4-1 through 4-18.
93 Entropy Environmentalists, Inc. Sampling and Analysis of Butadiene at a Synthetic
Rubber Plant. EPA Contract No. 68-02-4442. U.S. Environmental Protection Agency,
Atmospheric Research and Exposure Assessment Laboratory, Quality Assurance Division,
1988. pp. 3-5.
94 Hendricks, W.D., and G.R. Schultz. A Sampling and Analytical Method for Monitoring
Lowppm Air Concentrations of 1,3-Butadiene. Appl. Ind. Hyg., 1(4): 186-190, 1986.
95 Fajen, J.M., D.R. Roberts, L.J. Ungers, and E.R. Krishnan. Occupational Exposure of
Workers to 1,3-Butadiene. Environmental Health Perspectives. 86:11-18, 1990.
96 Blackley, C. (Radian Corporation) and R. Zweidinger (U.S. Environmental Protection
Agency) Telephone communication, May 10, 1994.
97 Blackley, C. (Radian Corporation) and P. Gabele (U.S. Environmental Protection Agency).
Telephone communication, May 10, 1994.
98. U.S. EPA. Butadiene Measurement Technology. EPA 460/3-88-005. Ann Arbor,
Michigan: U.S. Environmental Protection Agency, Office of Mobile Source Air Pollution
Control, 1988. pp. 1-23, Al-15, Bl-5, Cl-3.
99. Lee, F.S., and D. Schuetzle. Sampling, Extraction, and Analysis of Polycyclic Aromatic
Hydrocarbons from Internal Combustion Engines. In: Handbook of Polycyclic Aromatic
Hydrocarbons, A. Bjorseth, ed. New York, New York: Marcel Dekker, Inc., 1985. p. 30.
100. Hoekman, S.K. Improved Gas Chromatography Procedure for Speciated Hydrocarbon
Measurements of Vehicle Emissions. Journal of Chromatography, 639:239-253, 1993.
9-8
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APPENDIX A
EMISSION FACTOR SUMMARY TABLE
-------
TABLE A-l SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODE
SCC/AMS Code and
Description
2-02-001-01
Internal Combustion
Engines - Industrial
2-03-001-01
Internal Combustion
Engines - Commercial/
Industrial
3-01
Butadiene Dimers
3-01
Butadiene-furfural
Cotrimers
3-01
1,4-Hexadiene
Emissions Source
Distillate Oil/Diesel,
Reciprocating
Distillate Oil/Diesel,
Reciprocating
Process Vents
Equipment Leaks
Process Vents
Equipment Leaks
Equipment Leaks
Control Device
Uncontrolled
Uncontrolled
Controlled
Uncontrolled
Controlled
Controlled
Uncontrolled
Controlled
Controlled
Uncontrolled
Emission Factor"
Rangeb Mean
<0000391 Ib/MMBtu
(O.017 ng/J)
<.0000391 Ib/MMBtu
(<0.017 ng/J)
0.030 lb/tonc
(0.015 kg/Mg)
1.54 lb/tonc
(0.77 kg/Mg)
4.3 tons/yr"
(3.9 Mg/yr)
440 lb/tonc
(220 kg/Mg)
440 lb/tonc
(220 kg/Mg)
1.1 tons/yf
(0.5 Mg/yr)
59.3 tons/yr0
(53.8 Mg/yr)
67.7 tons/yr0
(61.4 Mg/yr)
Factor
Rating
E
E
U5
U5
U5
U5
U5
U5
U5
U5
-------
TABLE A-1 CONTINUED
3-01
Sulfolane
3-01
Tetrahydrophthalic
Anhydride/ Acid
3-01-026
SB Copolymer
Production
3-01-026
SB Copolymer
Production
3-01-026
SB Copolymer
Production
3-01-026
SB Copolymer
Production
3-01-026
SB Copolymer
Production
Emissions Source Control Device
Equipment Leaks Controlled
Uncontrolled
Equipment Leaks Controlled
Uncontrolled
Process vents Controlled
Uncontrolled
Equipment leaks Uncontrolled
Wastewater Controlled
Other liquid waste Controlled
Solid waste Controlled
Emission
Rangeb
1.8- 14.7 tons/yr*
(1.6-13.3 Mg/yr)
1.8- 14.7 tons/}'!*
(1.6-13.3 Mgtyr)
—
0.00024 - 94.34 lb/tond
(0.000 12 -47. 17 kg/Mg)
0.124- 94.34 lb/tond
(0.062 -47. 17 kg/Mg)
0.11 - 23.59 tons/yrd
(0.10 -21.40 Mg/yr)
0 - <10 lb/tond
(0 - <5 kg/Mg)'
<0.02 lb/tond
(<0.01 kg/Mg)
0 - <0.02 lb/tond
(0 - <0.01 kg/Mgf
Factor"
Mean
—
2.4 tons/yr0
(2.2 Mg/yr)
2.4 tons/yr0
(2.2 Mg/yr)
7.10 lb/tond
(3.55 kg/Mg)
14.20 lb/tond
(7.10 kg/Mg)
7.28 tons/yr*
(6.60 Mg/yr)
0.30 lb/tond
(0.1 5 kg/Mg)
<0.02 lb/tond
(<0.01 kg/Mg)
<0.02 lb/tond
(<0.01 kg/Mg)
Factor
Rating
U5
U5
U5
U5
D
D
D
D
D
D
-------
I ABLE A-1 CONTINUED
SCC/AMS Code and
Description Emissions Source
3-01-026 Process vents
Polybutadiene
Production
3-01-026 Equipment leaks
Polybutadiene
Production
3-01-026 Wastewater
Polybutadiene
Production
3-01-026 Solid waste
Polybutadiene
Production
3-01-026 Process vents
Neoprene Production
3-01-026 Equipment leaks
Neoprene Production
Control Device
Controlled
Uncontrolled
Controlled
Uncontrolled
Controlled
Uncontrolled
Controlled
Uncontrolled
Controlled
Uncontrolled
Controlled
Uncontrolled
Emission
Rangeb
0.00008 - 36.06 lb'/tonf
(0.00004 - 18.03 kg/Mg)
0.0032 - 36.06 lb/tonf
(0.0016 - 18.03 kg/Mg)
4.04-31.42tons/yrf
(3.66 - 28.50 Mg/yr)
4.04-31.42tons/yrf
(3.66 - 28.50 Mg/yr)
0 - 0.74 lb/tonf
(0 - 0.38 kg/Mg)
0 - 0.74 lb/tonr
(0 - 0.38 kg/Mg)
0 lb/tonf
(0 kg/Mg)
0 lb/tonf
(0 kg/Mg)
0.32 - 6.78 lb/tonc
(0.16 -3.89 kg/Mg)
0.40 - 24.18 lb/tonc
(0.20 - 12.09 kg/Mg)
1.03 - 4.88 tons/yr0
(0.93 - 4.43 Mg/yr)
1.03 - 4.88 tons/yf
(0.93 - 4.43 Mg/yr)
Factor*
Mean
6.14 lb/tonf
(3.07 kg/Mg)
8.96 lb/tonf
(4.48 kg/Mg)
10.41 tons/yi'
(9.44 Mg/yr)
10.41 tons/y/
(9.44 Mg/yr)
0.24 lb/tonf
(0.12 kg/Mg)
0.24 lb/tonf
(0.12 kg/Mg)
0 lb/tonf
(0 kg/Mg)
0 lb/tonf
(0 kg/Mg)
4.04 lb/tonc
(2.02 kg/Mg)
12.28 lb/tonc
(6. 14 kg/Mg)
2.95 tons/yf
(2.68 Mg/yr)
2.95 tons/yrc
(2.68 Mg/yr)
Factor
Rating
U5
U5
U5
U5
U5
U5
U5
U5
E
E
E
E
-------
TABLE A-l CONTINUED
SCC/AMS Code and
Description Emissions Source
3-01-026 Process \enls
Nitrile Elastomer
Production
3-01-026 Equipment leaks
Nitrile Elastomer
Production
3-01-026 Secondary sources
Nitrile Elastomer
Production
3-01-026 Equipment Leaks
Butadiene-vinylpyridine
Latex
3-01-153 Process Vents
Butadiene Cylinders
Equipment Leaks
3-01-153 Process vents
Butadiene Production -
C4 Stream Production
Control Device
Controlled
Uncontrolled
Uncontrolled
Controlled
Uncontrolled
Controlled
Controlled
Uncontrolled
Controlled
Uncontrolled
Uncontrolled
Emission
Rangeb
0.0004 - 17.80 Ib/ton0*
(0.0001 - 8.90 kg/Mg)
0.030 - <50 Ib/ton0-8
(0.01 - <25 kg/Mg)
0.43 - 18.67 toas/yf*
(0.39 - 16.93 Mg/yr)
0.002 - 0.018 Ib/ton0-8-1
(0.001 - 0.009 kg/Mg)
0.002 - 0.018 Ib/ton0-8-1
(0.001 -0.009 kg/Mg)
—
—
—
—
—
0.0054 lb/tond
(0.0027 kg/Mg)
Factor"
Mean
~ 4 Ib/ton0-8-11
(~ 2 kg/Mg)
~ 16 Ib/ton0-8-"
(~ 8 kg/Mg)
8.74 tons/yr0-8
(7.93 Mg/yr)
0.010 Ib/ton0-8-1
(0.005 kg/Mg)
0.010 Ib/ton0-8-1
(0.005 kg/Mg)
0.61 tons/yr0
(0.55 Mg/yr)
43.2 lb/tonc
(21.6 kg/Mg)
43.2 lb/tonc
(21.6 kg/Mg)
<0.11 tons/yr*
(<0.1 Mg/yr)
<0.11 tons/yr0
(<0.1 Mg/yr)
...
Rating
E
E
E
E
E
U5
U5
U5
U5
U5
E
-------
TABLE A-1 CONTINUED
>
LTt
SCC/AMS Code and
Description Emissions Source
3-01-153 Wasteuater
Butadiene Production -
Recovery Process
3-01-153 Solid \\aste
Butadiene Production -
Recovery Process
3-01-153-01 Process vents
Butadiene Production -
Recovery Process
3 -0 1 - 1 53 -80 Equipment leaksj
Butadiene Production -
Recovery Process
3-01-254 Process vents
Adiponitrile Production
3-01-254 Secondary sources
Adiponitrile Production
3-01-254-20 Equipment leaks
Adiponitrile Production
Control Device
Controlled
Controlled
Controlled
Uncontrolled
Controlled
Controlled
Uncontrolled
Controlled
Uncontrolled
Uncontrolled
Emission
Rangeb
0.00068 - 4.4 lb/tond
(0.00034 - 2.2 kg/Mg)
-«
0.0068 - 0.0550 lb/tond
(0.0034 - 0.0275 kg/Mg)
0.0322 - 0.6872 lb/tond
(0.0161 - 0.3436 kg/Mg)
455 tons/yrd
(407 Mg/yr)
0.12 Ib/ton^
(0.06 kg/Mg)
5.84 - 6.30 Ib/ton^
(2.92 -3. 15 kg/Mg)
0.016 - 0.024 Ib/tond4!
(0.008 -0.0 12 kg/Mg)
0.0 16- 0.024 Ib/ton"-8
(0.008 - 0.012 kg/Mg)
2.72 - 5.25 tons/yr*"
(2.47 - 4.76 Mg/yr)
Factor*
Mean
0.936 lb/tond
(0.468 kg/Mg)
5.542xlO-7 lb/tond
(4.988xlO-7 kg/Mg)
0.03141b/tond
(0.0157 kg/Mg)
0.4652 lb/tond
(0.2326 kg/Mg)
_-.
0.12 lb/ton^
(0.06 kg/Mg)
6.08 Ib/ton^
(3.04 kg/Mg)
0.02 lb/tondj!
(0.01 kg/Mg)
0.02 lb/tond-B
(0.01 kg/Mg)
3.99 tons/yr*-8
(3.62 Mg/yr)
Factor
Rating
E
E
E
E
E
U5
U5
U5
U5
U5
-------
TABLEA-1. CONTINUED
SCC/AMS Code and
Description Emissions Source
3-04-004-03 Blast furnace outlet
Secondary lead
^ Rotary furnace outlet
5-01-007-01 Influent
Wastewater treatment
facility
5-03-002-03 Chunk tires
Open Burning of Tires
Shredded tires
6-41 Process Vents
Methylmethacrylate-
butadiene-styrene
Resins
Equipment Leaks
6-41 Process vents
ABS Production
6-41 Equipment leaks
ABS Production
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Controlled
Uncontrolled
Controlled
Uncontrolled
Controlled
Uncontrolled
Controlled
Uncontrolled
0.78
(0.32
4.0-
(3.6-
0.16-
(0.08
6.50-
(3.25
1.21 -
(1.10
1.21 -
(1.10
Emission
Rangeb
- 1.54 lb/ton
- 0.63 kg/Mg)
___
—
...
—
17.4 tons/yi*
- 15.8 Mg/yr)
—
10.66 lb/toncjt
- 5.33 kg/Mg)
11.281b/toncjt
- 5.64 kg/Mg)
3.50 tons/yf*
-3. 17 Mg/yr)
3.50 tons/yf*
-3. 17 Mg/yr)
Factor"
Mean
1.16 lb/ton
(0.48 kg/Mg)
0.13 lb/ton
(0.05 kg/Mg)
1.7 x 103 lb/ton
(771 g/kg)
234.28 lb/1,000 tons
(117.14mg/kg)
277.95 lb/1,000 tons
(138.97 mg/kg)
1.8 lb/tonc
(0.9 kg/Mg)
17.2 lb/tonc
(8.6 kg/Mg)
—
17.4 tons/yi*
(15.8 Mg/yr)
4.22 lb/tonc*
(2. 11 kg/Mg)
9.48 Ib/ton0-"
(4.74 kg/Mg)
2.36 tons/yr0-*
(2.14 Mg/yr)
2.36 tons/yf*
(2.14 Mg/yr)
Factor
Rating
C
C
U5
C
C
U5
U5
U5
U5
E
E
E
E
-------
TABLE A-1. CONTINUED
SCC/AMS Code and
Description
6-46-300-01
Polyvinyl chloride
6-84-350
Dodecanedioic Acid
22-01-001-000
Light-Duty Gas Vehicle
22-01-020-000
Light-Duty Gas Truck 1
22-01-040-000
Light-Duty Gas Truck 2
22-01-060-000
Light-Duty Gas Truck
22-01-070-000
Heavy -Duty Gas
Vehicle
22-01-080-000
Motorcycle
22-30-001-000
Light-Duty Diesel
Vehicle
Emissions Source
Suspension process,
entire plant
Equipment Leaks
Mobile
Mobile
Mobile
Mobile
Mobile
Mobile
Mobile
Control Device
Uncontrolled
Controlled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor"
Rangeb Mean
4.6 x 10-4 Ib/ton
(2.1 x 10-4g/kg)
5.73 tons/yr°
(5.2 Mg/yr)
5.73 tons/yi*
(5.2 Mg/yr)
2 x 10 ' Ib/mile
(0.01 g/mile)
4 x 10 5 Ib/mile
(0.02 g/mile)
6 x 10"' Ib/mile
(0.03 g/mile)
4 x 10-5 Ib/mile
(0.02 g/mile)
1 x 10 4 Ib/mile
(0.06 g/mile)
6 x 10 5 Ib/mile
(0.03 g/mile)
2 x 10 ' Ib/mile
(0.01 g/mile)
Factor
Rating
U5
U5
U5
D
D
D
D
D
D
D
-------
TABLE A-1 CONTINUED
oo
SCC/AMS Code and
Description
22-30-060-000
Light-Duty Diesel
Truck
22-30-070-000
Heavy-Duty Diesel
Vehicle
22-60-001-010
Off-Road Motorcycles
22-60-001-020
Snowmobiles
22-60-001-030
All Terrain Vehicles
(ATV's)
22-60-001-050
Golf Carts
22-60-001-060
Specialty Vehicles Carts
22-60-002-006
Tampers/Rammers
22-60-002-009
Plate Compactors
22-60-002-021
Paving Equipment
22-60-002-033
Bore/Drill Rigs
Emissions Source
Mobile
Mobile
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor*
Rangeb Mean
— 2 x 10 5 Ib/mile
(0.01 g/mile)
1 x 10'4 Ib/mile
(0.05 g/mile)
16.38 g/hr1
2.978 g/hp-hr1
16.38 g/hr1
16.38 g/hr1
16.38 g/hr1
5.678 g/hp-hr1
5.678 g/hp-hr1
5.678 g/hp-hr1
5.678 g/hp-hr1
— Factor
Rating
D
D
E
E
E
E
E
E
E
E
E
-------
TABLE A-1 CONTINUED
SCC/AMS Code and
Description
22-60-003-010
Aerial Lifts
22-60-003-020
Forklifts
22-60-003-030
Sweepers/Scrubbers
22-60-003-040
Other General Industrial
Equipment
> 22-60-004-010
vo Lawn Mowers
22-60-004-015
Tillers <5 hp
22-60-004-020
Chain Saws <4 hp
22-60-004-025
Trimmers/Edgers/ Brush
Cutters
22-60-004-030
Leaf Blowers/ Vacuums
22-60-004-035
Snowblowers
22-60-004-050
Shredders <5 hp
22-60-004-070
Commercial Turf
Equipment
Emissions Source
2-stroke gas, exhaust
2-stroke gas, crank case
2-stroke gas, exhaust
2-stroke gas, crank case
2-stroke gas, exhaust
2-stroke gas, crank case
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor8 ,
Rangeb Mean
0.059 g/hp-hr-11
0.019 g/hp-hT-"
0.05.9 g/hp-hT-"
0.019 g/hp-hi"1-11
0.056 g/rip-nrm'n
0.019 g/hp-hi™-"
4.056 g/hp-hi"
5.678 g/hp-hr
5.678 g/hp-hr1
8.135 g/hp-hr1
6.131 g/hp-hr1
5.878 g/hp-hr1
5.678 g/hp-hr1
5.678 g/hp-hr1
5.678 g/hp-hr1
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLEA-1. CONTINUED
SCC/AMS Code and
Description
22-60-004-075
Other Lawn and Garden
Equipment
22-60-006-005
Generator Sets
22-60-006-010
Pumps
22-60-006-020
Gas Compressors
22-60-007-005
Chain Saws >4 hp
22-60-008-010
Terminal Tractors
22-65-001-010
Off-Road Motorcycles
22-65-001-030
All Terrain Vehicles
(ATV's)
22-65-001-040
Minibikes
22-65-001-050
Golf Carts
Emissions Source
2-stroke gas. exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, crank case
2-stroke gas, exhaust
2-stroke gas, crank case
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor1
Rangeb Mean
5.678 g/hp-hr1
5.678 g/hp-hr1
0.1 17 g/hp-hr1
0.018 g/hp-hr1
0.084 g/hp-hi"1-11
0.018 g/hp-hr"1-11
4.15 g/hp-hr1
0.059 g/hp-hr™-"
0.013 g/hp-hi"1-11
1.95 g/hi"
0.429 g/hi"
2.73 g/hr1
0.429 g/hr1
2.73 g/hr1
0.429 g/hr1
2.73 g/hr1
0.429 g/hr1
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-1 CONTINUED
SCC/AMS Code and
Description
22-65-001-060
Specialty Vehicles Carts
22-65-002-003
Asphalt Pavers
22-65-002-006
Tampers/Rammers
22-65-002-009
Plate Compactors
22-65-002-015
• Rollers
I— >
22-65-002-021
Paving Equipment
22-65-002-024
Surfacing Equipment
22-65-002-027
Signal Boards
22-65-002-030
Trenchers
22-65-002-033
Bore/Drill Rigs
22-65-002-036
Excavators
Emissions Source
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor8
Rangeb Mean
2.73 g/hr1
0.429 g/hr1
0.127 g/hp-hi"
0.028 g/hp-hr"
0.177g/hp-hr1
0.028 g/hp-hr1
0.177 g/hp-hr1
0.028 g/hp-hr1
0.253 g/hp-hr1
0.04 g/hp-hr1
0.177 g/hp-hr1
0.028 g/hp-hr1
0.177 g/hp-hr1
0.028 g/hp-hr1
0.177 g/hp-hr1
0.028 g/hp-hr1
0.127 g/hp-hi"
0.028 g/hp-hr11
0.127g/hp-hrn
0.028 g/hp-nr"
0.127g/hp-hf
0.028 g/hp-hr"
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
IABI.KA-1 CONTINUED
SCC/AMS Code and
Description
22-65-002-039
Concrete/Industrial
Saws
22-65-002-042
Cement and Mortar
Mixers
22-65-002-045
Cranes
22-65-002-054
Crushing/Proc.
Equipment
22-65-002-057
Rough Terrain Forklifts
22-65-002-060
Rubber Tire Loaders
22-65-002-066
Tractors/Loaders/
Backhoes
22-65-002-072
Skid Steer Loaders
22-65-002-078
Dumpers/Tenders
22-65-002-081
Other Construction
Equipment
Emissions Source
4-stroke gas. exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor*
Rangeb Mean
0.177 g/hp-hr1
0.028 g/hp-hr1
0.177 g/hp-hr1
0.028 g/hp-hr1
0.127 g/hp-hi"
0.028 g/hp-hr11
0.127 g/hp-hr"
0.028 g/hp-hr11
0.127 g/hp-hr"
0.028 g/hp-hr"
0.108 g/hp-hr"
0.024 g/hp-hr"
0.1 27 g/hp-hr"
0.028 g/hp-hr"
0.127 g/hp-hr"
0.028 g/hp-hr"
0.177 g/hp-hr1
0.028 g/hp-hr1
0.127 g/hp-hr"
0.028 g/hp-hr"
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-1. CONTINUED
SCC/AMS Code and
Description
22-65-003-010
Aerial Lifts
22-65-003-020
Forklifts
22-65-003-030
Sweepers/Scrubbers
22-65-003-040
Other General Industrial
Equipment
22-65-003-050
Other Material
Handling Equipment
22-65-004-010
Lawn Mowers
22-65-004-015
Tillers <5 hp
22-65-004-025
Trimmers/Edgers/ Brush
Cutters
22-65-004-030
Leaf Blowers/ Vacuums
22-65-004-035
Snowblowers
Emissions Source
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor*
Rangeb Mean
0.13 g/hp-hr"
0.029 g/hp-hr"
0.13 g/hp-hr"
0.029 g/hp-hr"
0.13 g/hp-hr"
0.029 g/hp-hr"
0.13 g/hp-hr"
0.027 g/hp-hr"
0.13 g/hp-hr"
0.027 g/hp-hr"
1.029 g/hp-hr1
0.162 g/hp-hr1
1.029 g/hp-hr1
0.162g/hp-hrJ
0.66 g/hp-hr1
0.104 g/hp-hr1
0.53 g/hp-hr1
0.083 g/hp-hr1
1.029 g/hp-hr1
0.162 g/hp-hr1
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-1 CONTINUED
SCC/AMS Code and
Description
22-65-004-040
Rear Engine Riding
Mowers
22-65-004-045
Front Mowers
22-65-004-050
Shredders <5 hp
22-65-004-055
Lawn and Garden
Tractors
22-65-004-060
Wood Splitters
22-65-004-065
Chippers/Stump
Grinders
22-65-004-070
Commercial Turf
Equipment
22-65-004-075
Other Lawn and Garden
Equipment
22-65-005-010
2-Wheel Tractors
22-65-005-015
Agricultural Tractors
Emissions Source
4-stroke gas. exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor"
Rangeb Mean
0.254 g/hp-hr1
0.04 g/hp-hr1
0.254 g/hp-hr1
0.04 g/hp-hr1
1.029 g/hp-hr1
0.162 g/hp-hr1
0.257 g/hp-hr1
0.04 g/hp-hr1
1.029 g/hp-hr1
0.162 g/hp-hr1
0.735 g/hp-hi"
0.162 g/hp-hr"
0.257 g/hp-hr1
0.04 g/hp-hr1
1.029 g/hp-hr1
0.162 g/hp-hr1
0.15 g/hp-hr1
0.024 g/hp-hr1
0.107g/hp-hrn
0.024 g/hp-hi"
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-1 CONTINUED
SCC/AMS Code and
Description
22-65-005-020
Combines
22-65-005-030
Agricultural Mowers
22-65-005-035
Sprayers
22-65-005-040
Tillers >5 hp
22-65-005-045
Swathers
22-65-005-050
Hydro Power Units
22-65-005-055
Other Agricultural
Equipment
22-65-006-005
Generator Sets
22-65-006-010
Pumps
22-65-006-015
Air Compressors
22-65-006-025
Welders
Emissions Source
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor8
Rangeb Mean
0.14 g/hp-hr"
0.031 g/hp-hr"
0.199 g/hp-hr1
0.031 g/hp-hr1
0.14 g/hp-hr"
0.031 g/hp-hr"
1.029 g/hp-hr1
0.162 g/hp-hr1
0.14 g/hp-hr"
0.031 g/hp-hr"
0.196 g/hp-hr1
0.031 g/hp-hr1
0.14 g/hp-hr"
0.031 g/hp-hr"
0.259 g/hp-hr1
0.041 g/hp-hr1
0.259 g/hp-hr1
0.041 g/hp-hr1
0.259 g/hp-hr1
0.041 g/hp-hr1
0.259 g/hp-hr1
0.041 g/hp-hr1
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-1 CONTINUED
SCC/AMS Code and
Description
22-65-006-030
Pressure Washers
22-65-007-010
Shredders >5 hp
22-65-008-005
Aircraft Support
Equipment
22-65-008-010
Terminal Tractors
> 22-70-001-060
~ Specialty Vehicles Carts
22-70-002-003
Asphalt Pavers
22-70-002-006
Tampers/Rammers
22-70-002-009
Plate Compactors
22-70-002-012
Concrete Pavers
22-70-002-015
Rollers
Emissions Source
4-stroke gas. exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor* .
Rangeb Mean
0.259 g/hp-hr1
0.041 g/hp-hr1
0.254 g/hp-hr1
0.04 g/hp-hr1
0.13 g/hp-hr"
0.029 g/hp-hr"
0.13 g/hp-hr"
0.029 g/hp-hr"
0.019 g/hr
0.0003 g/hr
0.01 g/hp-hr
0.0002 g/hp-hr
0.00 g/hp-hr
0.00 g/hp-hr
0.013 g/hp-hr
0.0003 g/hp-hr
0.018 g/hp-hr
0.0003 g/hp-hr
0.013 g/hp-hr
0.0003 g/hp-hr
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
I ABLE A-1 CONTINUED
SCC/AMS Code and
Description
22-70-002-018
Scrapers
22-70-002-021
Paving Equipment
22-70-002-024
Surfacing Equipment
22-70-002-027
Signal Boards
22-70-002-030
^ Trenchers
-0
22-70-002-033
Bore/Drill Rigs
22-70-002-036
Excavators
22-70-002-039
Concrete/Industrial
Saws
22-70-002-042
Cement and Mortar
Mixers
22-70-002-045
Cranes
Emissions Source
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor8
Rangeb Mean
0.011 g/hp-hr°
0.0002 g/hp-hr°
0.016 g/hp-hr
0.0003 g/hp-hr
0.00 g/hp-hr
0.00 g/hp-hr
0.019 g/hp-hr
0.0003 g/hp-hr
0.025 g/hp-hr0
0.0005 g/hp-hr0
0.023 g/hp-hr0
0.0005 g/hp-hr0
0.011 g/hp-hr0
0.0002 g/hp-hr0
0.023 g/hp-hr0
0.0005 g/hp-hr0
0.016 g/hp-hr
0.0003 g/hp-hr
0.02 g/hp-hr0
0.0005 g/hp-hr0
— Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-1 CONTINUED
SCC/AMS Code and
Description
22-70-002-048
Graders
22-70-002-051
Off-Highway Trucks
22-70-002-054
Crushing/Proc.
Equipment
22-70-002-057
Rough Terrain Forklifts
> 22-70-002-060
£j Rubber Tire Loaders
22-70-002-063
Rubber Tire Dozers
22-70-002-066
Tractors/Loaders/
Backhoes
22-70-002-069
Crawler Tractors
22-70-002-072
Skid Steer Loaders
22-70-002-075
Off-Highway Tractors
Emissions Source
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor8
Rangeb Mean
0.025 g/hp-hr°
0.0005 g/hp-hr0
0.013 g/hp-hr0
0.0003 g/hp-hr0
0.023 g/hp-hr0
0.0005 g/hp-hr0
0.027 g/hp-hr0
0.0005 g/hp-hr0
0.013 g/hp-hr0
0.0003 g/hp-hr0
0.013 g/hp-hr0
0.0003 g/hp-hr0
0.022 g/hp-hr0
0.0005 g/hp-hr0
0.02 g/hp-hr0
0.0005 g/hp-hr0
0.034 g/hp-hr0
0.0006 g/hp-hr0
0.039 g/hp-hr0
0.0008 g/hp-hr"
- Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-l CONTINUED
>
SCC/AMS Code and
Description
22-70-002-078
Dumpers/Tenders
22-70-002-081
Other Construction
Equipment
22-70-003-010
Aerial Lifts
22-70-003-020
Forklifts
, 22-70-003-030
Sweepers/Scrubbers
22-70-003-040
Other General Industrial
Equipment
22-70-003-050
Other Material
Handling Equipment
22-70-004-040
Rear Engine Riding
Mowers
22-70-004-055
Lawn and Garden
Tractors
22-70-004-060
Wood Splitters
Emissions Source
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor"
Rangeb Mean
0.013 g/hp-hr0
0.0003 g/hp-hr0
0.023 g/hp-hr0
0.0005 g/hp-hr0
0.025 g/hp-hr0
0.0005 g/hp-hr0
0.025 g/hp-hr0
0.0005 g/hp-hr0
0.025 g/hp-hr0
0.0005 g/hp-hr0
0.025 g/hp-hr0
0.0005 g/hp-hr0
0.025 g/hp-hr0
0.0005 g/hp-hr0
0.019 g/hp-hr
0.0003 g/hp-hr
0.019 g/hp-hr
0.0003 g/hp-hr
0.0192 g/hp-hr
0.0003 g/hp-hr
- Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-l CONTINUED
K)
O
SCC/AMS Code and
Description
22-70-004-065
Chippers/Stump
Grinders
22-70-004-075
Other Lawn and Garden
Equipment
22-70-005-015
Agricultural Tractors
22-70-005-020
Combines
22-70-005-025
Balers
22-70-005-035
Sprayers
22-70-005-040
Tillers >5 hp
22-70-005-045
Swathers
22-70-005-050
Hydro Power Units
22-70-005-055
Other Agricultural
Equipment
Emissions Source
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor"
Rangeb Mean
0.019 g/hp-hr
0.0003 g/hp-hr
0.019 g/hp-hr
0.0003 g/hp-hr
0.036 g/hp-hr0
0.0006 g/hp-hr0
0.02 g/hp-hr0
0.0005 g/hp-hr0
0.038 g/hp-hr
0.0006 g/hp-hr
0.038 g/hp-hr
0.0006 g/hp-hr
0.019 g/hp-hr
0.0003 g/hp-hr
0.014 g/hp-hr
0.0003 g/hp-hr
0.036 g/hp-hr
0.0006 g/hp-hr
0.029 g/hp-hr
0.0006 g/hp-hr
Partnr
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-1 CONTINUED
SCC/AMS Code and
Description
22-70-006-005
Generator Sets
22-70-006-010
Pumps
22-70-006-015
Air Compressors
22-70-006-025
Welders
22-70-006-030
Pressure Washers
22-70-007-015
Skidders
22-70-007-020
Fellers/Bunchers
22-70-008-005
Aircraft Support
Equipment
22-70-008-010
Terminal Tractors
22-82-005-005
Vessels iv/Inboard
Engines
Emissions Source
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, crank case
2-stroke gas, exhaust
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor*
Rangeb Mean
0.019 g/hp-hr
0.0003 g/hp-hr
0.019 g/hp-hr
0.0003 g/hp-hr
0.019 g/hp-hr
0.0003 g/hp-hr
0.019 g/hp-hr
0.0003 g/hp-hr
0.019 g/hp-hr
0.0003 g/hp-hr
0.013 g/hp-hr0
0.0003 g/hp-hr0
0.013 g/hp-hr0
0.0003 g/hp-hr0
0.025 g/hp-hr0
0.0005 g/hp-hr0
0.025 g/hp-hr0
0.0005 g/hp-hr0
11.358g/gal"
Factor
Rating
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-l CONTINUED
K>
SCC/AMS Code and
Description
22-82-005-010
Vessels w/Outboard
Engines
22-82-005-015
Vessels w/Sterndrive
Engines
22-82-005-025
Sailboat Auxiliary
Outboard Engines
22-82-010-005
Vessels vv/Inboard
Engines
22-82-010-010
Vessels w/Outboard
Engines
22-82-010-015
Vessels w/Sterndrive
Engines
22-82-010-020
Sailboat Auxiliary
Inboard Engines
22-82-010-025
Sailboat Auxiliary
Outboard Engines
22-82-020-005
Vessels w/Inboard
Engines
Emissions Source
2-stroke gas, exhaust
2-stroke gas, exhaust
2-stroke gas, exhaust
4-stroke gas, exhaust
4-stroke gas, exhaust
4-stroke gas, crank case
4-stroke gas, exhaust
4-stroke gas, exhaust
4-stroke gas, exhaust
4-stroke gas, crank case
Diesel, exhaust
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor"
Rangeb Mean
11.358g/gaT
11.358g/gaT
11.358g/gaT
1.413 g/gaT
1.71 g/gaP
0.376 g/gal"
1.413 g/gaT
1.413 g/gaP
1.71 g/gal"
0.376 g/gal"
0.39 g/gal
Rating
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-1. CONTINUED
N)
U>
SCC/AMS Code and
Description
22-82-020-010
Vessels w/Outboard
Engines
22-82-020-015
Vessels w/Sterndrive
Engines
22-82-020-020
Sailboat Auxiliary
Inboard Engines
22-82-020-025
Sailboat Auxiliary
Outboard Engines
26-10-030-000
Yard Waste
28-01-500-000
Land Clearing/Burning
28-10-001-000
Forest Fires
Emissions Source
Diesel, exhaust
Diesel, crank case
Diesel, exhaust
Diesel, exhaust
Diesel, exhaust
Diesel, crank case
Biomass burning
Biomass burning
Fine wood
Small wood
Large wood (flaming)
Large wood (smoldering)
Live vegetation
Control Device
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Uncontrolled
Emission Factor"
Rangeb Mean
0.39 g/gal
0.008 g/gal
0.39 g/gal
1.959 g/gal
1.959 g/gal
0.039 g/gal
0.40 Ib/ton
(0.198 g/kg)
0.32 Ib/ton
(0.163 g/kg)
0.24 Ib/ton (0.12 g/kg)
0.24 Ib/ton (0.1 2 g/kg)
0.24 Ib/ton (0.1 2 g/kg)
0.90 Ib/ton (0.45 g/kg)
0.52 Ib/ton (0.26 g/kg)
Factor
Rating
E
E
E
E
E
E
U4
U4
U4
U4
U4
U4
U4
-------
I ABU- A-l CONTINUED
SCC/AMS Code and
Description
28-10-001-000
Forest Fires (continued)
28-10-005-000
Slash (pile) Burning
28-10-015-000
Prescribed Burning
(Broadcast)
28-10-040-000
Rocket engine testing
Emissions Source Control Device
Duff (flaming)
Duff (smoldering)
Biomass burning Uncontrolled
Fine wood Uncontrolled
Small wood
Large wood (flaming)
Large wood (smoldering)
Live vegetation
Duff (flaming)
Duff (smoldering)
Mobile Uncontrolled
Emission Factor"
Rangeb Mean
0.24 Ib/ton (0.1 2 g/kg)
0.90 Ib/ton (0.45 g/kg)
0.32 Ib/ton
(0.163 g/kg)
0.24 Ib/ton (0.12 g/kg)
0.24 Ib/ton (0.12 g/kg)
0.24 Ib/ton (0.1 2 g/kg)
0.90 Ib/ton (0.45 g/kg)
0.52 Ib/ton (0.26 g/kg)
0.24 Ib/ton (0.1 2 g/kg)
0.90 Ib/ton (0.45 g/kg)
0.14 Ib/ton
(0.057 kg/Mg)
Factor
Rating
U4
U4
U4
U4
U4
U4
U4
U4
U4
U4
C
"Factors are generally expressed as Ib (kg) butadiene emitted per ton (Mg) produced and tons (Mg) emitted per year, unless otherwise noted.
bRanges are based on actual emissions reported by the facilities. Thus, values include controls whenever they have been implemented.
'Assumes production capacity of 100 percent.
dAssumes production capacity of 80 percent.
TJpper value used to prevent disclosing confidential operating capacity.
'Assumes production capacity of 81 percent.
8Only incomplete data on emissions were available, therefore, values underestimate emissions.
hUpper value used to prevent disclosing confidential operating capacity.
'Lower end of range is for one solid waste stream; upper end includes solid waste, wastewater and contaminated cooling water.
Total number of components is 79,430: 60 percent flanges, 29 percent liquid valves, 8 percent gas valves, and 3 percent all others combined.
kData from two facilities are specific to the emulsion process; the third is assumed to use the same.
'Adjusted for in-use effects using small utility engine data.
"Emission factors for 4-stroke propane-fueled equipment.
"Adjusted for in-use effects using heavy duty engine data.
-------
TABLE A-1 CONTINUED
"Exhaust HC adjusted for transient speed and/or transient load operation
"—" means no data available.
NJ
-------
APPENDIX B
ESTIMATING METHODS FOR NATIONAL BUTADIENE EMISSION SOURCES
-------
EMISSIONS FROM ON-ROAD MOBILE SOURCES
Basis for Calculation
To estimate national butadiene emissions for this report, the butadiene emission factor
presented in the MVATS1 was used with VMT data from the Federal Highway
Administration's Highway Statistics 19922 This approach is similar to the one used to
estimate emissions from on-road mobile sources for State Implementation Plan (SIP)
inventories (Procedures for Emission Inventory Preparation Volume IV: Mobile Sources,
19923). Table B-l summarizes 1992 VMT data and butadiene emissions estimates for each
State using the OMS's composite emission factor of 0.023 g of butadiene/mile.
Example Calculation
Annual Emissions = (0.023 g butadiene/VMT) x (4.5762xl010 VMT) x
for Alabama (1.10231136 ton/Mg)
= 1,161 ton of butadiene
B-l
-------
TABLE B-l. 1992 ON-ROAD BUTADIENE EMISSIONS
State
Alabama
Alaska -
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Dist. of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
1992 Vehicle Miles Travelled
(millions)
45,762
3,841
35,047
23,081
262,548
28,927
26,459
6,892
3,562
114,311
77,904
8,066
10,764
87,642
57,072
23,926
24,163
38,062
33,853
12,151
41,896
47,348
84,219
41,162
26,239
53,254
8,525
Emissions in tons (Mg)
1,161 (1,053)
97 (88)
888 (806)
584 (530)
6,657 (6,039)
733 (665)
671 (609)
175 (159)
90 (82)
2,898 (2,629)
1,975 (1,792)
205 (186)
273 (248)
2,222 (2,016)
1,447(1,313)
606 (550)
613 (556)
965 (875)
859 (779)
308 (279)
1,063 (964)
1,200 (1,089)
2,135 (1,937)
1,044 (947)
665 (603)
1,350 (1,225)
216 (196)
(continued)
B-2
-------
TABLE B-l. CONTINUED
State
Nebraska
Nevada .
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Total
1992 Vehicle Miles Travelled
(millions)
14,621
10,897
10,067
59,410
18,452
109,881
67,538
6,072
95,221
35,119
27,926
89,200
7,676
35,049
7,218
49,994
163,329
16,307
6,019
63,447
49,386
16,478
47,628
6,217
2,239,828
Emissions in tons (Mg)
370 (336)
277 (251)
256 (232)
1,506 (1,366)
467 (424)
2,786 (2,527)
1,712 (1,553)
154 (140)
2,414 (2,190)
891 (808)
708 (642)
2,262 (2,052)
195 (177)
888 (806)
183 (166)
1,268 (1,150)
4,141 (3,757)
413 (375)
152 (138)
1,608 (1,459)
1,252 (1,136)
418 (379)
1,207 (1,095)
158 (143)
56,786 (51,517)
Source: Reference 2.
B-3
-------
EMISSIONS FROM NON-ROAD MOBILE SOURCES
Basis for Calculation:
National emissions for butadiene were taken directly from the NEVES report.4 "In use"
estimates for butadiene were taken from two inventories: A, which is an EPA-developed
inventory; and B, which is an inventory prepared by trade associations. The values were
averaged to calculate the national emission estimates.
Calculation:
Butadiene estimate for the:
A inventory - 47,816 tons/year
B inventory - 35,949 tons/year
National Annual = 47,816 + 35,949
Emissions 2
= 41,883 tons/year
B-4
-------
EMISSIONS FROM AIRCRAFT
Basis for Calculation
To estimate national emissions from aircraft, hydrocarbon emission indices for representative
fleet mixes are provided in the emissions inventory guidance document Procedures for
Emissions Inventory Preparation; Volume IV: Mobile Sources* The hydrocarbon emission
indices are 0.394 pounds per LTO (0.179 kg per LTO) for general aviation and 1.234 pounds
per LTO (0.560 kg per LTO) for air taxis.
The butadiene fraction of the hydrocarbon total can be estimated by using the percent weight
factors from SPECIATE.6 It is assumed in this report that half of the general aviation fleet
is equipped with piston engines and the other half is equipped with turbine engines, such that
these two emission factors are averaged. Because air taxis have larger engines and more of
the fleet is equipped with turboprop and turbojet engines than is the general aviation fleet, the
percent weight factor is somewhat different from the general aviation emission factor. To
approximate a butadiene percent weight factor for air taxis, the commercial and general
aviation (piston) percent weight factors were averaged.
Because there are no aggregated hydrocarbon emission indices for commercial or military
aircraft, national emissions estimates for butadiene for these aircraft categories cannot be
estimated without considerable detailed activity data (i.e., fleet mix and associated LTOs).
To estimate national butadiene emissions for general aviation and air taxis, FAA air traffic
activity data7 (LTO) were applied to the hydrocarbon emission indices to estimate total
national hydrocarbon emissions. The appropriate weight percent butadiene factor were
applied to the total national hydrocarbon emission values, yielding the national butadiene
emission estimate for general aviation and air taxis. These emission estimates are presented
in Table 6-6. Note that in this approach emissions were estimated for aircraft airport activity
B-5
-------
EMISSIONS FROM AIRCRAFT, CONTINUED
only; in-flight emissions cannot be calculated without considerable detailed data. In addition,
this estimate does not include any aircraft activity occurring at non-FAA control towered
airports.
Calculation - General Aviation
General Aviation = (0.394 Ibs hydrocarbon/LTO) x (ton/2,000 Ibs) x
Emissions (19,584,898 LTOs in 1993) x (1.57 weight % butadiene)
= 61 tons
Calculation - Air Taxis
Air Taxi Emissions = (1.234 Ibs hydrocarbon/LTO) x (ton/2000 Ibs) x (4,418,836 LTOs in
1993) x (1.69 weight % butadiene)
= 46 tons
Calculation - Total
National Butadiene = 61 ton/yr of butadiene + 46 ton/yr of butadiene
Emissions Estimate
= 107 ton/yr of butadiene
B-6
-------
EMISSIONS FROM BUTADIENE PRODUCTION
Basis for Calculation
The 1992 TRI data were used as an estimate of national emissions from butadiene production
facilities.8 The TRI butadiene values (in Ib/yr) reported by the 11 butadiene production
facilities listed in Table 4-1 of this document were summed to give an estimate of the
butadiene emissions from production facilities nationwide. The estimated national emissions
of butadiene from butadiene production facilities are 191 tons/yr (163 Mg/yr).
B-7
-------
EMISSIONS FROM MAJOR BUTADIENE USERS
Basis for Calculation
The 1992 TRI data were used to estimate national emissions from major butadiene users.8
All facilities with their primary SIC Codes reported as 28XX, industries within the Chemicals
and Allied Products classification, were assumed to represent major users of butadiene. Some
of the miscellaneous butadiene uses described in Section 7.0 may also be included, but
because differentiating would be difficult and the contribution to national emissions from the
miscellaneous uses is considered to be small, extracting these from the TRI data was not
done.
The facility SIC Codes reported included the following:
28 Chemicals and allied products
2812 Alkalies and chlorine
2819 Industrial inorganic chemicals, nee
2821 Plastics materials, synthetic resins, and nonvulcanizable elastomers
2822 Synthetic rubber (vulcanizable elastomers)
2865 Cyclic organic crudes and intermediates, and organic dyes and pigments
2869 Industrial organic chemicals, nee
2879 Pesticides and agricultural chemicals, nee
2891 Adhesives and sealants
2899 Chemicals and chemical preparations, nee
To avoid double-counting butadiene production facility emissions (butadiene production
facilities also fall under the 2869 SIC Code), the total for the 11 facilities (191 tons/yr (163
Mg/yr)) was subtracted from the total for the 28XX SIC Codes (1,596 tons/yr (1,448 Mg/yr)).
The estimated national emissions of butadiene from major butadiene users are 1,405 tons/yr
(1,275 Mg/yr).
B-8
-------
EMISSIONS FROM MISCELLANEOUS OTHER BUTADIENE SOURCES
Basis for Calculation
The 1992 TRI data also included other source categories that were not otherwise identified as
butadiene sources during the revision of this document.8 These facilities fall into one of the
following SIC Codes. There were two facilities for which no SIC Code was reported, and
one facility used an SIC Code, 2641, for which the 1987 Standard Industrial Classification
Manual9 has no description.
2046 Wet corn milling
2369 Girl's, children's, and infant's outerwear, nee
2621 Paper mills
3312 Steel works, blast furnaces (including coke ovens), and rolling mills
3579 Office machines, nee
8731 Commercial physical and biological research
The butadiene emissions reported by each of these facilities were summed to total national
emissions of butadiene from miscellaneous other butadiene sources of 106 tons/yr (96 Mg/yr).
B-9
-------
EMISSIONS FROM PETROLEUM REFINING
Basis for Calculation
While the Petroleum Refineries NESHAP provides emissions estimates for VOCs and total
HAPs at 190 facilities, emission estimates are not available for specific HAPs, such as
butadiene.10 Therefore, 1992 TRI data were used as estimates of national emissions from
petroleum refining.8 Petroleum refining is represented by SIC Code 2911. Based on the TRI
data, the estimated national emissions of butadiene from petroleum refining are 219 tons/yr
(241 Mg/yr).
B-10
-------
EMISSIONS FROM SECONDARY LEAD SMELTING
Basis for Calculation
As part of the background information for developing the proposed and final NESHAP for the
secondary lead smelting industry, emissions data were collected for 1,3-butadiene and other
species of organic HAP during an EPA-sponsored test program at three representative
smelters.11 These data were used to calculate total controlled organic HAP emissions for
each of the 23 secondary lead smelters known to exist in the United States.
The emission estimates assumed that organic HAP emissions from each smelter were
controlled to the level required by the final NESHAP. Total estimated organic HAP
emissions from this industry under the final NESHAP are 552 ton/yr (508 Mg/yr). The final
NESHAP will reduce organic HAP emissions 71 percent from a 1990 baseline of 1,905 ton/yr
(1,728 Mg/yr).
The emissions test data were also used to estimate a ratio of 1,3-butadiene to total organic
HAP emissions for each of the three smelters for which test data were available:
ton 1,3-butadiene/ton organic HAP
East Penn Manufacturing Company: 0.337
Schuylkill Metals: 0.252
Tejas Resources: 0.131
Average: 0.240
The data from East Penn and Schuylkill are from blast furnaces and the data from Tejas are
from a rotary furnace. The difference in ratios cannot be explained by any of the parameters
that were monitored during the testing program or any of the differences in
B-ll
-------
EMISSIONS FROM SECONDARY LEAD SMELTING, CONTINUED
feed stocks used at these smelters; all three smelters used essentially the same feed stocks.
Example Calculation
National Emissions = (0.240 tons of 1,3-butadiene/ton organic HAP) x
Estimate (560 tons organic HAP/yr)
= 134.4 ton/yr (121.9 Mg/yr)
B-12
-------
EMISSIONS FROM OPEN BURNING OF BIOMASS
Basis for Calculation
Emission factors for butadiene emissions from forest fires and prescribed burning were
obtained from a 1993 Office of Research and Development project on Puget Sound and an
inventory prepared by Darold Ward and Janice Peterson for the USDA Forest Service.12'13
The emission factors vary according to fuel type (i.e., flaming versus smoldering wood or
duff or live vegetation) and are presented in Section 7.0 of this document.
A national activity level for biomass burning (i.e., prescribed burning and forest fires) was
obtained from a final report for the national emission inventories compiled for
Section 112(c)(6) pollutants, prepared by Radian Corporation for the EPA.14 The total
biomass burning in prescribed burning was documented as 42 million tons, and the total
biomass burned in forest fires was documented as 53 million tons.14 Because no information
was available to characterize, on a national basis, the percentages of the specific types of
fuels burned in forest fires and prescribed burning, certain assumptions were made in
calculating national emissions from the emission factors. The national estimate is calculated
based on flaming wood and duff and smoldering wood and duff. It was assumed that, on a
national basis, during prescribed burns and forest fires 75 percent of the biomass (wood and
duff) is burned under flaming conditions and 25 percent of the biomass (wood and duff) is
burned under smoldering conditions.
The following calculations were carried out to determine national butadiene emissions
from forest fires. However, the national emissions from prescribed burning were obtained
from a prescribed fire emissions inventory developed from Ward and Peterson's
methodology.13
B-13
-------
EMISSIONS FROM OPEN BURNING OF BIOMASS, CONTINUED
Example Calculation:
Annual
National Emissions
Annual
National Emissions
Annual
National Emissions
emissions from forest fires
[(1.2 x 10"4 tons/ton flaming wood and duff burned) x
(39,750,000 tons flaming wood and duff burned in forest fires/yr)] +
[(4.5 x 10"4 tons/ton smoldering wood and duff burned) x
(13,250,000 tons smoldering wood and duff burned in forest
fires/yr)]
10,733 tons/yr (9,737 Mg/yr)
emissions from prescribed burning
9,198 tons/yr (8,345 Mg/yr)
emissions from biomass burning
10,733 tons/yr + 9,198 tons/yr
19,931 tons/yr (18,082 Mg/yr)
B-14
-------
REFERENCES
1. U.S. EPA. Motor Vehicle-Related Air Toxics Study. Section 7.0 - 1,3-Butadiene.
EPA-420-R-93-005. Ann Arbor, Michigan: U.S. Environmental Protection Agency,
Office of Mobile Sources, 1993. pp. 7-1 to 7-7.
2. U.S. Department of Transportation. Highway Statistics. Washington, D.C.: Federal
Highway Administration, 1993. p. 208
3. U.S. EPA. Mobile Sources Procedures for Emission Inventory Preparation, Volume IV:
Mobile Sources. EPA-450/4-81-026d (Revised). Ann Arbor, Michigan.
U.S. Environmental Protection Agency, Office of Mobile Sources, 1992. p. 176.
4. U.S. EPA. Non-Road Engine and Vehicle Emission Study. 21A-2001. Washington,
D.C.: U.S. Environmental Protection Agency, Office of Air and Radiation, 1991.
pp. M-53, O-53.
5. U.S. EPA. Mobile Sources Procedures for Emission Inventory Preparation, Volume IV:
Mobile Sources. Section 5.0 - Emissions from Aircraft. EPA-450/4-81-026d (Revised).
Ann Arbor, Michigan: U.S. Environmental Protection Agency, Office of Mobile
Sources, 1992. p. 176.
6 U.S EPA. Volatile Organic Compound/Paniculate Matter Speciation Data System
(SPEC/ATE). Version 1.5. Research Triangle Park, North Carolina: U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards, October 1992.
7 Federal Aviation Administration. Air Traffic Activity. Office of Management Systems,
1993 Table 1-7.
8. U.S EPA 1992 Toxic Chemical Release Inventory (SARA 313) Database. Washington,
D.C.. U.S. Environmental Protection Agency, Office of Toxic Substances, 1993.
9. U.S Executive Office of the President. Standard Industrial Classification Manual.
Washington, D.C.. Government Printing Office, Office of Management and Budget,
1987
10. Zarate, M. (Radian Corporation). Memorandum to J. Durham (U.S. Environmental
Protection Agency) concerning "Process Vent Information Collection Request Data
Quality Analysis," August 25, 1993.
11. U.S. EPA. Final Background Information Document for Secondary Lead NESHAP.
EPA-450/R-94-024a. Research Triangle Park, North Carolina: U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards, June 1994.
B-15
-------
12. Campbell, D.L. and J. Mangino (Radian Corporation). "Evaluation and Improvement of
the Puget Sound Toxic Air Contaminants Emissions Inventory." Technical Note. EPA
Contract No. 68-D1-0031. Washington, D.C.: U.S. Environmental Protection Agency,
Office of Research and Development, May 1994.
13. Peterson, J. and D. Ward. An Inventory of Particulate Matter and Air Toxic Emissions
from Prescribed Fires in the United States for 1989. U.S. Department of Agriculture,
Forest Service, 1989. pp. 1-16.
14. Radian Corporation. Draft final memorandum to U.S. Environmental Protection Agency
concerning Inventory Plan for Section 112(c)(6) Pollutants. September 23, 1993.
B-16
-------
APPENDIX C
FACILITY-SPECIFIC EMISSIONS DATA FROM EPA SECTION 114 RESPONSES
-------
APPENDIX C
FACILITY-SPECIFIC EMISSIONS DATA
FROM EPA SECTION 114 RESPONSES
Tables C-l through C-25 contain the capacity and emissions data that formed the basis
for the emission factor ranges and ranges of annual emissions presented in the main text.
Capacity data were compiled from responses to Section 114 requests or literature values if
available. Most of the emissions data are from responses to Section 114 requests in 1984.
Inconsistencies with the text are due to facility changes in ownership and/or in the production
process since 1984. The emission values, therefore, may no longer reflect the current status
of the industry. Furthermore, reported emissions were not supplied for every emission point
identified, nor were all emission points identified by each facility.
Emission factors for each emission point were calculated by dividing the reported
emissions by the facility's capacity, modified to reflect actual production. In instances where
the use of facility production capacity in an emission factor might reveal company-
confidential information, the emissions data were not used to calculate the ranges. In the
absence of facility-reported capacity values, literature values may have been used.
Equipment leak emission estimates were derived from 1984 data supplied by facilities
in Section 114 responses. Using the procedure described in Appendix D and average CMA
emission factors, ranges of annual emissions were calculated. Equipment count data for the
miscellaneous category were unavailable, therefore estimates are based on the SOCMI
emission factors as reported in the summary memoranda.
C-l
-------
TABLE C-1. BUTADIENE PRODUCTION FACILITIES FOR WHICH
1984 EMISSION DATA ARE AVAILABLE
Company
Location
Capacity in 1984
tons/yr (Mg/yr)
Amoco Chemicals Company
Cain Chemical Company1"
Cain Chemical Company0
Exxon Chemicals Company
Mobil Chemical Company
Shell Chemical Company
Texas Chemical Company
Texas Petrochemicals Corp.
Chocolate Bayou, TX
Channelview, TX
Chocolate Bayou, TX
Corpus Christi, TX
Baton Rouge, LA
Baytown, TX
Beaumont, TX
Deer Park, TX
Norco, LA
Port Neches, TX
Houston, TX
90,400 (82,000)a
350,500 (318,000)
67,200 (61,000)a
110,200 (100,000)a
155,400 (141,000)
120,200 (109,000)
29,800 (27,000)a
400,100 (363,000)
250,200 (227,000)
179,700 (163,000)
400,100 (363,000)d
Source. Reference 1.
'Values taken from the literature.
Tormerly DuPont de Nemours and Company.
'Formerly El Paso Products Company.
"250.200 tons/yr (227.000 Mg/yr) from the recovery process, 149,900 tons/yr (136.000 Mg/yr) from the
dch\ drogenation process.
C-2
-------
TABLE C-2 BUTADIENE EMISSIONS (1984) FROM PROCESS VENTS AT
OLEFINS AND BUTADIENE PRODUCTION FACILITIES '
C4 Stream Production Emissions
in tons/yr (Mg/yr)3
Recovery Process Emissions
in tons/yr (Mg/yr)b
Company Uncontrolled
Facility A
Facility B
Facility C
Facility D 0.3 (0.3)
Facility E
Facility F
Facility G
Facility Hd
Controlled Control Device Uncontrolled
—
Flare
___
N/A None
1.5(1.4)
—
67.7(61.4)
68.8 (62.4)
Controlled
—
—
—
—
N/A
—
0.7 (0.6)
5.5 (5.0)
Control Device
Flare
Flare
Flare
—
None
Flare
Boiler/Flare
Boiler/Flare
Source: Reference 1.
"C4 stream producdon means production of a mixed-C4 stream as a coproduct from the manufacturer of ethy lene and other
alkenes in an olefins plant.
""Recovery process means recovery of butadiene from a mixed-C4 stream.
The combination was assigned an overall efficiency of 99 percent.
dSource of the mixed-C4 stream is unknown.
^Reduction efficiency based on facility reported information.
"—" means no data available.
N/A means not applicable.
-------
TABLE C-3. SUMMARY OF BUTADIENE EMISSIONS (1987) FROM
EQUIPMENT LEAKS AT NINE PRODUCTION FACILITIES
Equipment Component
Pumps - liquid
Compressors
Flanges
Valves - gas
Valves - liquid
Pressure relief devices
Open-ended lines
Sample points0
Total:
Number of
Components
376
17
47,277b
6,315
23,233
428
1,744
40
79,430
Emissions4
(tons/yr)
74
0.0002
51
24
260
45
0.73
0.37
460
(Mg/yr)
67
0.0002
46
22
230
41
0.67
0.34
410
aAssumes 80 percent of production capacity (taken as 8,760 hours of operations per year). Emissions
rounded to two significant figures.
bAlthough only 11,428 flanges were included in the study, a ratio of 1.6:1 flanges:valves is generally accepted.
The total number of flanges upon which the emissions estimate is based is, therefore,
1(6.315 + 23,233) x 1.6] = 47,277.
""Emission factor was taken from reference 1, p.5-16.
C-4
-------
TABLE C-4. BUTADIENE EMISSIONS (1984) FROM SECONDARY SOURCES
AT BUTADIENE PRODUCTION FACILITIES USING THE
RECOVERY FROM A MIXED-C4 STREAM PROCESS
Emissions in tons/yr (Mg/yr) Controls/Destination
Company
Facility B
Facility D
Facility E
Facility G
Facility H
Facility I
Facility J
Facility K
Wastewater
Negligible
6.1(5.5)
0.03 (0.03)
—
18.1 (16.4)
0.18(0.16)
320 (290)
—
Solid Waste Wastewater
Negligible"
Emissions routed to flare, air
strip or steam strip
Negligible Emissions routed to flare, air
strip or steam strip for recovery
or to flare
Onsite NPDES, disposal wells
Aeration lagoon
Biological treatment
Biological treatment, discharge
Biological treatment
Solid Waste
—
Incineration
Incineration
Offsite landfill
Offsite landfill
—
—
Landfill, disposal well
Source: Reference 1.
"Reported as "minor."
bEstimated at 4.43 x 105 Ib/yr (3.99 x 10'5 Mg/yr).
"—" means no data available.
-------
TABLE C-5. STYRENE-BUTADffiNE ELASTOMER AND LATEX PRODUCTION
FACILITIES FOR WHICH 1984 EMISSIONS DATA ARE AVAILABLE
Company
Elastomer
American Synthetic"
B. F. Goodrich0
Copolymer Rubber
Firestone
GenCorp
Goodyear
Uniroyal0
Latex
Berg-Warner6
Dow Chemical
Dow Chemical
Dow Chemical
Dow Chemical
Dow Chemical
GenCorp
Goodyeare
Goodyear
W R Grace
Polysar
Reichhold (DE)
Reichhold (GA)
Unocal
Location
Louisville, KY
Port Neches, TX
Baton Rouge, LA
Lake Charles, LA
Odessa, TX
Houston, TX
Port Neches, TX
Washington, WV
Dalton, GA
Freeport, TX
Gates Ferry, CT
Midland, MI
Pittsburgh, CA
Mogadore, OH
Akron, OH
Calhoun, GA
Owensboro, KY
Chattanooga, TN
Cheswold, DE
Kensington, GA
La Mirada, CA
Capacity in 1984
tons/yr (Mg/yr)
lll,200b(100,000)b
d
232,600b(211,000)b
132,300" (120,000)"
95,900b (87,000)"
d
201,700" (183,000)"
d
d
d
d
d
d
66,100 (60,000)
d
d
3,300 (3,000)
167,500 (152,000)
65,000 (59,000)
58,400 (53,000)
19,800 (18,000)
Source: Reference 2.
"Facility was mothballed in 1984.
'Dry weight.
'B.F. Goodnch and Uniroyal are now Ameripol Synpol.
dCompany-confidential.
Tacility's operating status in 1988 unknown.
C-6
-------
TABLE C-6 Bl' I ADII-NL EMISSIONS (1984) FROM PROCESS VENTS
A I SB COF'OLYMER PRODUCTION FACILITIES2
n
Company
Elastomer
Facility A
Facility B
Facility C
Facility D
Facility E
Facility F
Facility G
Latex
Facility H
Facility 1
Facility J
Uncontrolled Emissions
Vent Location tons/yr (Mg/yr)
Recovery process
Butadiene recovery
Butadiene absorber \ent
Tank farm, purification
reactor, desolventization
Recovery area absorber vent
Process vessels (storage
blending, coagulation, crumb
washing)
Dryers
Butadiene recovery
Latex Al
Latex A2
Latex B
Vent stack
Monomer mix tanks, recover}
tank
29 (26)
463 (420)
22 (20)
88 (80)b
4.7 (4.3)
66 (60.0)a
11(10.0)
139(126)
127(115)
127(115)
518(469.8)
d
d
Controlled Emissions Control Efficiency
tons/yr (Mg/yr) Control Device (%)
2.9 (2.6)
23.1 (21.0)
0.02 (0.02)"
,.8<,.6f
0.7 (0.6)
N/A
N/A
7.0 (6.3)b
N/A
N/A
44.5 (40.4)
285 (259)
11.4(10.3)
Absorber
Kerosene absorber
Boiler
Flare
Absorber
None
None
Kerosene scrubbers
None
None
Pressure condenser
d
d
90
95
99.9
98
86
0
0
95
0
0
91.4
d
d
-------
TABLE C-6. CONTINUED
Company
Elastomer
Facility K
Facility L
Facility M
Facility N
Facility O
O Facility P
°° Facility Q
Facility R
Facility S
Vent Location
Reactors, strippers
Process scrubber
Latex process
Latex process and tanks
Central vacuum flare stack
Latex stripping
Butadiene recovery
Vent gas absorber
Reactor
Mix tank
Reactor recovery storage
Recycle butadiene receiver
Stripping vacuum pump
exhaust
Process
Uncontrolled Emissions
tons/yr (Mg/yr)
d
d
d
d
628 (570)
0.6 (0.5)
36 (33)
17 (15)
104.7 (95.0)
20.1 (18.2)
5.5 (5.0)e
15.4 (14.0)<
45.0 (40.8)
325 (295)
Controlled Emissions
tons/yr (Mg/yr)
10.8 (9.8)
30.0 (27.0)
5.3 (4.8)
5.6 (5.1)
12.6(11.4)
N/A
3.7 (3.3)
0.3 (0.3)
N/A
N/A
0.1 (0.1)
N/A
N/A
6.5 (5.9)
Control Device
d
d
d
Flare
None
Condenser
Scrubber
None
None
Flare
None
None
Flare
Control Efficiency
(%)
d
d
d
98
0
90
98
0
0
98°
0
0
98
-------
TABLE C-6. (CONTINUED)
n
Company
Elastomer
Facility T
Facility U
Vent Location
Waste vent gas
Vacuum pump discharge
Stream jet discharge
Unknown
Uncontrolled Emissions
tons/yr (Mg/yr)
60 (54.0)
226.3 (205.3)
11.9(10.8)
Unknown
Controlled Emissions
tons/yr (Mg/yr)
N/A
N/A
N/A
Unknown
Control Device
None
None
None
Incineration
Control Efficiency
(%)
0
0
0
Unknown
Source: Reference 2.
"Emissions shown are for both SB copolymer and nitrile rubber production.
Emissions shown are for both SB copolymer and polybutadiene production.
'Facility reported a higher efficiency but did not support it with test data.
Information for facilities on control devices is considered confidential.
'Estimates exclude reported emissions for pressure relief discharges of 0.1 tons/yr (0.1 Mg/yr).
N/A = not applicable.
-------
TABLE C-7. BUTADIENE EMISSIONS (1984) FROM EQUIPMENT LEAKS
AT SB COPOLYMER PRODUCTION FACILITIES
Uncontrolled Emissions'
Company tons/yr (Mg/yr) Control Status
Elastomer
Facility A
Facility B
Facility C
Facility D
Facility E
Facility F
Facility G
Latex
Facility H
Facility I
Facility J
Facility K
Facility L
Facility M
Facility N
Facility O
Facility P
Facility Q
Facility R
Facility T
6.2 (5.6)
8.5 (7.7)
14.3 (13)b
4.0 (3.6)
74 (67)
23 (21)b
14 (13)c
15 (14)
5.0 (4.5)
1.5 (1.4)
0.98 (0.89)
2.9 (2.6)
2.1 (1.9)
5.8 (5.3)
4.6 (4.2)
4.7 (4.3)
0.11 (0.10)
14(13)
2.2 (2.0)
PRDs vented to a flare
Rupture discs for PRDs
Rupture discs
Rupture discs and flare for PRDs
None reported
Rupture discs and flare for PRDs
Most PRDs have rupture discs vented
None reported
None reported
None reported
None reported
Some rupture discs
Rupture discs
None reported
Rupture discs for PRDs
None reported
None reported
Some rupture discs
Most PRDs have rupture discs
Source: References 2 and 3.
"Calculated using 1984 equipment counts and average CMA emission factor. Emissions rounded to two
significant figures.
"The emissions are for both SB copolymer and nitrile rubber production.
The emissions are for both SB copolymer and polybutadiene production.
PRDs= Pressure relief devices.
C-10
-------
TABLE C-8 BUTADIENE EMISSIONS (1984) FROM SECONDARY SOURCES
AT SB COPOLYMER PRODUCTION FACILITIES2
O
Company
Elastomer
Facility A
Facility B
Facility C
Facility D
Facility E
Facility G
Latex
Facility H
Facility I
Facility J
Facility K
Facility L
Facility M
Facility N
Emissions in tons/yr (Mg/yr)
Wastewater Other Liquid Waste
0 0
0.4 (0.4)
0.9 (0.8) a
0 0
13.8 (12.5) a
0
0 0
0
0
0 0.008 (0.007)
0
0
0.00002 (0.00002)
from:
Solid Waste
0
,
Waste Treatment
None
Landfill, primary and secondary treatment
0.0007 (0.0006)
0
2.2 (2.0)
0
0
0
0
0
0
—
—
" Biotreaftnent, incineration, landfill
Unknown
a Biotfeatment, landfill
Unknown
Unknown
NPDES permit, landfill
Unknown
b BiotrSatment incineration of liquid
landfarm solids
Biotreatment, landfill
Solar pond
Equalization, settling, discharge to
waste,
POTW
-------
TABLE C-8 CONTINUED
Emissions in tons/yr (Mg/yr) from:
Company
Elastomer
Facility O
Facility P
Facility Q
Facility R
Facility T
Wastewater
14.4° (13.1)c
8.6 (7.8)
Negligible11
26.4 (24.0)
Negligible11
Other Liquid Waste Solid Waste
c c
—
—
—
Negligible11 Negligible11
Waste
Discharge to POTW
Aerated lagoon
Biotreatment, aerated
City sewer*
Biotreatment
Treatment
lagoon
>L Source: Reference 2.
to
"Emissions are for both SB copolymer and nitrile rubber production.
""Emissions occur off-site from an incinerator stack.
Tacility did not report emissions separately for each of the four production processes on-site.
dOnly trace amounts of butadiene reported in waste.
Tacility had two units in production; waste treatment at Unit #2 is confidential.
"—" means no information available on the source.
-------
TABLE C-9. POLYBUTADIENE PRODUCTION FACILITIES FOR WHICH
1984 EMISSIONS DATA ARE AVAILABLE
Capacity in 1985
Company Location tons/yr (Mg/Yr)
American Synthetic Rubber Louisville, KY 69,400* (63,000)a
Arco Chemicalb Channelview, TX 7,500 (6,800)
Borg-Warner Ottawa, IL
Firestone n.,300- (, ,0,000)'
Goodyear
Phillips
Polysar
Beaumont, TX
Borger, TX
Orange, TX
70,500* (64,000)a
c
Source: Reference 4.
"Value taken from the literature.
facility's operating status in 1988 unknown.
'Company confidential.
^Facility coproduced SBS elastomer and polybutadiene rubber, but was primarily dedicated to SB elastomer.
C-13
-------
n
TABLE C-IO BUTADIENE EMISSIONS (1984) FROM PROCESS VENTS
AT POLYBUTAD1ENE PRODUCTION FACILITIES4
Company
Facility A
Facility B
Facility C
Facility D
Facility E
Facility F
Vent Locations
Recovery process
Acetone column vent
Vacuum system vent
Flashers
Plantwide
Two plant vents
Polymerization reactors
Kerosene scrubbing
Uncontrolled
Emissions
tons/yr (Mg/yr)
0.09 (0.08)
36.5(33.1)
73.0(66.2)
48.9 (44.4)
22.0 (20)
568(515)
5.5(5)
27.6 (25)
Controlled
Emissions
tons/yr (Mg/yr)
0.002 (0.002)
N/A
N/A
4.4 (4.0)
0.4 (0.4)
11.4(10.3)
0.1 (0.1)
0.6 (0.5)
Control Device
Butadiene absorber, flare
None
None
Butadiene recovery
Flare
Flare
Flare
Flare
Control
Efficiency
(%)
97.5
N/A
N/A
91
98
98
98
98
Source: Reference 4.
"Company reported greater than 98-percent control efficiency, but did not provide supporting test data.
N/A = not applicable.
-------
TABLE C-ll. BUTADIENE EMISSIONS (1984) FROM EQUIPMENT LEAKS
AT POLYBUTADIENE PRODUCTION FACILITIES
Company
Facility A
Facility B
Facility D
Facility E
Facility F
Facility G
Uncontrolled Emissions
tons/yr (Mg/Yr)a
4.1 (3.7)
5.8(5.3)
32.0 (29)
10.5 (9.5)
5.7 (5.2)
4.9 (4.4)
Source: References 3 and 4.
"Calculated using 1984 equipment counts and average CMA emission factors. Emissions rounded to two
significant figures.
C-15
-------
TABLE C-12. BUTADIENE EMISSIONS (1984) FROM SECONDARY SOURCES
AT POLYBUTADIENE PRODUCTION FACILITIES
Company
Facility B
Facility C
Facility F
Wastewater
—
0
21.3 (19.3)
Source
tons/yr (Mg/yr)
Solid Waste Waste Treatment
0 . Landfill
— * Activated sludge
— Lagoon
Source: Reference 4.
"Facility listed solid waste as a source but provided no data.
"—" means no data available.
C-16
-------
TABLE C-13. ADIPONITRILE PRODUCTION FACILITIES FOR WHICH
1984 EMISSIONS DATA ARE AVAILABLE
Capacity in 1984
Facility Location tons/yr (Mg/Yr)
DuPont Orange, TX 231,500(210,000)"
DuPont Victoria, TX 146,500 (132,900)
Source: Reference 5.
'Value taken from the literature.
C-17
-------
TABLE C-14 BUTADIENE EMISSIONS (1984) FROM PROCESS VENTS
AT ADIPON1TRILE PRODUCTION FACILITIES5
Uncontrolled
Emissions
Company Vent Location tons/yr (Mg/yr)
Facility A Recycle purge 540.1(490)
Butadiene dryer
Facility B Recycle purge 363.8(330)
Butadiene dryer 4.9 (4.4)
0 Jets
00 Second reactor
Refining
Controlled Emissions Control
tons/yr (Mg/yr) Device
10.8 (9.8) Flare
Boiler
7.3 (6.6) Flare
0.004 (0.004) Boiler
Boiler
Boiler
Boiler
Control Efficiency
98
—
98
99.9
99.9
99.9
99.9
Source: Reference 5.
'Facility reported a higher efficiency but did not provide supporting test data.
"—" means no data available.
-------
TABLE C-15. BUTADIENE EMISSIONS (1984) FROM EQUIPMENT LEAKS
AT ADIPOMTRILE PRODUCTION FACILITIES
Uncontrolled
Emissions
Company tons/yr (Mg/yr)a Controls
Facility 'A
Facility B
5.3 (4.8)
2.8 (2.5)
Ambient monitoring,1" double mechanical
seals, some PRDs routed to a flare.
Quarterly LDAR, ambient monitoring, double
mechanical seals.
Source: References 3 and 5.
"Calculated using 1984 equipment counts and average CMA emission factors. Emissions rounded to two
significant figures.
bAmbient monitoring in the vicinity was being used to detect elevated VOCs, potentially indicating leaks.
PRDs = pressure relief devices.
LDAR = leak detection and repair program.
C-19
-------
TABLE C-16. BUTADIENE EMISSIONS (1984) FROM SECONDARY SOURCES
AT ADIPONITRILE PRODUCTION FACILITIES
Uncontrolled
Source Emissions
Facility Description tons/yr (Mg/Yr)
Facility A Waste tank 2.2(2.0)
Butadiene separator blowdown water —
Facility B Sump tank" —
Waste liquids" —
Wastewater 1.0 (0.9)
Source: Reference 5.
"Source was routed to a boiler with a 99.9-percent reduction efficiency.
"—" means no data reported.
C-20
-------
TABLE C-17. CHLOROPRENE/NEOPRENE PRODUCTION FACILITIES FOR
WHICH 1984 EMISSIONS DATA ARE AVAILABLE
Capacity in 1985"
Company tons/yr (Mg/Yr)
Denka 37,500 (34,000)
DuPont 47,400 (43,000)
Source: Reference 6.
"Values taken from the literature.
C-21
-------
TABLE C-18 BUTADIENE EMISSIONS (1984) FROM NEOPRENE PRODUCTION FACILITIES6
Process Vent Emissions
tons/yr (Mg/yr)
n
K)
KJ
Company Vent Location
Facility A DCB refining
DCB refining
DCB refining
Facility B DCB refining
DCB synthesis
Uncontrolled
5.3(4.8)
0.96(0.87)
1.06(0.96)
176(160)
397 (360)
Controlled
N/A
0.1 (0.1)
0.6(0.5)
N/A
7.9 (7.2)
Control Device
None
Absorber/-20°F
condenser
-20° F condenser
Water-cooled
condenser
Flare
Control
Efficiency
(%)
0
88.6
48.0
0
98
Equipment Leaks -
Uncontrolled"
tons/yr (Mg/yr)
1.03(0.93)
4.9 (4.4)
Source: Reference 6.
'Calculated using 1984 equipment counts and average CMA emission factors. Emissions rounded to two significant figures.
bCompany estimated a higher efficiency but did not provide supportive data.
N/A = Not applicable.
-------
TABLE C-19. ACRYLONITRILE-BUTADIENE-STYRENE RESIN PRODUCTION
FACILITIES FOR WHICH 1984 EMISSIONS DATA ARE AVAILABLE
Capacity in 1985"
Company Location tons/yr (Mg/Yr)
Goodyearb
Monsanto
Monsanto
Akron, OH
Addyston, OH
Muscatine, IA
165 (150)
177,500 (161,000)
57,500 (52,200)
Source: Reference 7.
'Values taken from the literature.
bGoodyear coproduced ABS with nitrite elastomer. About 3 percent was dedicated to production.
C-23
-------
TABLE C-20 BUTADIENE [-MISSIONS (1984) FROM ABS PRODUCTION FACILITIES7
n
K)
Process Vent Emissions
tons/yr (Mg/yr)
Company
Facility A
Facility B
Facility C
Vent Location
Spray dryer
Dewatering (1)
Polymerization (9)
Dewatering (1)
Dewatering (1)
Dewatering (1)
Tanks (3)
Tanks (6)
Coagul/Wash (7)
Compounding (9)
Polymerization (1)
Polymerization(l)
Uncontrolled
09(0.8)
Unknown
661(500)
<11(<10)
2.1(1.9)
2.1 (1.9)
10.0(9.0)
Unknown
Unknown
0
276 (250)
6.8(6.2)
Controlled
N/A
N/A
0.6(0.5)
<0.01 (<0.01)
N/A
N/A
N/A
Unknown
Unknown
N/A
2.8 (2.5)
N/A
Control Device
None
None
Flare
Boiler
None
None
None
Unknown
Unknown
None
Flare
None
Control
Efficiency (%)
0
0
99.9
99.9
0
0
0
Unknown
Unknown
0
99
0
Equipment Leaks -
Uncontrolled
tons/yr (Mg/yr)
Unknown
3.5 (3.2)
1.2(1.1)
(Continued)
-------
TABLE C-20 CONTINUED
Process Vent Emissions
tons/yr (Mg/yr)
p
lb
Company Vent Location3
Coagul/Wash (2)
Dewatering (4)
Compounding (1)
Tanks (5)
Source: Reference 7.
Uncontrolled
18.5 (16.8)
10.7 (9.7)
6.9 (6.3)
6.2 (5.6)
"Number in parenthesis indicates number of vents.
bCalculated from 1984 equipment counts and average CM A emission
Controlled
N/A
N/A
N/A
N/A
factors. Emissions
Control Device
None
None
None
None
Equipment Leaks
Control - Uncontrolled
Efficiency (%) tons/yr (Mg/yr)
0
0
0
0
rounded to two significant figures.
-------
TABLE C-21. NTTRILE ELASTOMER PRODUCTION FACILITIES FOR
WHICH 1984 EMISSIONS DATA ARE AVAILABLE
Capacity in 1985,
dry rubber or latex
Company Location tons/yr (Mg/Yr)
B. F. Goodrich" Akron, OH 0
Copolymer Baton Rouge, LA 7,500b (6,800)b
Goodyear Houston, TX 17,600 (16,000)
Goodyeaf Akron, OH 5,500 (5,000)
Sohiod Lima, OH
Uniroyal Chemical Co. Painesville, OH 18,000 (16,300)
Source: Reference 7.
"B. F. Goodrich closed its NBR facility in 1983. Facility still produced 8,377 tons/yr (7,600 Mg/yr) of
vinyl pyridine.
bValue taken from the literature.
Tacihty also produced about 165 tons/yr (150 Mg/yr) of ABS copolymer (3 percent of production).
facility's operating status in 1988 unknown.
'Company confidential.
C-26
-------
TABLE C-22 BUTADIENE EMISSIONS (1984) FROM NITRILE ELASTOMER PRODUCTION FACILITIES7
o
Process Vent Emissions tons/yr
(Mg/yr)
Company
Facility A
Facility Bc
Facility Cd
Facility Df
Facility E
Vent Location
Process A (46)
Butadiene absorber
Slowdown tank (1)
Coagulator(l)
Building (1)
Screening (1)
Dewatering(l)
Dryer (2)
Reactor (1)
Absorber (1)
Distillation (1)
Screen/coagulation (2)
Reactor (1)
Uncontrolled
60.6 (55)
<0 07 (<0.06)
35.3 (32)
42.3 (38.4)
3 2 (2.9)
—
...
—
—
—
...
16.5(15)
220.0 (200)
Controlled
2.4 (2.2)
O.001 (<0.001)
3.5(3.2)
—
—
—
—
—
—
—
—
1.7(1.5)
0.2 (0.2)
Control Device
Boiler
Boiler
Condenser
Chemical treatment
None
Chemical treatment
None
None
Flare
Flare
Flare
Steam stripper for acrylonitrile
Thermal oxidation
Control
Efficiency
96
99+
90
Unknown
0
Unknown
0
0
99.9
99.9
99.9
90 .
99.9
Equipment Leaks -
Uncontrolled1"
tons/yr (Mg/yr)
—
18.7(17)
—
—
0.43 (0.39)
-------
TABLE C-22. CONTINUED
o
K>
00
Process Vent Emissions tons/yr
(Mg/yr)
Company Vent Location8
Facility P Recycle receiver (1)
Steam jets (2)
Dryer (1)
Tanks (8)
Uncontrolled
3.3 (3.0)
Controlled
0.36 (0.33)
Control Device
Scrubber
Steam stripper for acrylonitrile
Steam stripper for acrylonitrile
Steam stripper for acrylonitrile
Control
Efficiency
89
90
90
90
Equipment Leaks
Uncontrolled11
tons/yr (Mg/yr)
7.2 (6.5)
Source: Reference 7.
"Number in parentheses indicates the number of vents of this type.
bCalculated from 1984 equipment counts and average CMA emission factors. Emissions rounded to two significant figures.
'Facility was also an SB copolymer producer; total facility emissions were reported. Emissions apportioned to NBR production based on percent
production resulting in nitrile elastomer~3 percent.
'"Facility was also an ABS copolymer producer; total facility emissions were reported. Emissions apportioned to NBR production based on percent
production resulting in nitrile elastomer~97 percent.
'Chemical treatment destroys residual acrylonitrile. The effect on butadiene is not known.
'Only equipment leaks emissions were apportioned using percent of capacity dedicated to nitrile elastomer.
"Facility was also an SB copolymer producer; total facility emissions were reported. Emissions apportioned to NBR production based on percent
production resulting in nitrile elastomer-5 percent.
"—" means no data available.
-------
TABLE C-23 MISCELLANEOUS USES OF BUTADIENE FOR WHICH
EMISSIONS DATA ARE AVAILABLE5
Company
Location
Product
Mode of Operation
1986 Design
Capacity
tons/yr (Mg/yr)
n
to
ArChem Company
B. F. Goodrich Company
Denka (Mobay Synthetics
Corporation)
DuPont
DuPont
Houston, TX
Akron, OH
Houston, TX
Beaumont, TX
Victoria, TX
Tetrahydrophthalic Batch
(THP) Anhydride
Butadiene-vinylpyridine Batch (on demand)
Latex
Kanaka Texas Corporation Bay port, TX
Phillips Chemical Company Borger, TX
THP Acid
1,4-Hexadiene
Dodecanedioic Acid
MBS Resins
Butadiene Cylinders0
Butadiene-furfural
Cotrimer0
Batch
Continuous
Continuous (2 weeks per
month due to low demand)
Batch
Batch
Continuous, intermittent,
about 65% of the time
568 (515)
Unknown
1,650 (1,500)
14,300b (13,000)b
535 (485)
50 (45)
Rohm and Haas Company
Shell Oil Company
Union Carbide
Louisville, KY
Norco, LA
Institute, WV
Sulfolane
MBS Resins
Sulfolane
Butadiene Dimers
Batch
Batch
Unknown
Continuous
Unknown
a
Unknown
7,200 (6,500)
Source: Reference 5.
"Company confidential.
bAccording to reference 4, capacity was due to increase to 26,500 tons/yr (24,000 Mg/yr) in cln operation in 1984, status unknown in 1987.
cln operation in 1984, status unknown in 1987.
-------
TABLE C-24 BUTADIENE EMISSIONS FROM PROCESS VENTS ASSOCIATED WITH
MISCELLANEOUS USES OF BUTADIENE 5'8'9
O
Chemical
Produced
Butadiene
cylinders
Butadiene dimers
Butadiene-furfural
cotrimer
Butadiene-
vinylpyridine latex
Dodecanedioic
acid
1,4-Hexadiene
Methyl
methacrylate-
butadiene-styrene
resins
Company
Facility A
Facility B
Facility A
Facility C
Facility D
Facility E
Facility F
Facility G
Vent Location
Process vents
Feedpot, rec\cle pot, reactor, and
three recovery stills
Reactor
Crude storage
Process vents
Dryer
Butadiene dryer + two jets
Reactor
Knockout pot
Reactor, stripper, recycle
condenser
Reactor
Coagulator
Dryer
Reactor
Uncontrolled
Emissions
tons/yr (Mg/yr)
11.6(10.5)
5.6 (5)
Unknown
10.9 (9.9)
353 (320)
6.6 (6.0)
220 (200)
27.2 (24.7)
Unknown
110(100)
6.6 (6.0)
6.6 (6.0)
1.0 (0.9)
Controlled
Emissions
tons/yr (Mg/yr)
N/A
0.1(0.1)
0
N/A
0.35 (0.32)
N/A
0.2 (0.2)
N/A
Unknown
0.1(0.1)
N/A
N/A
N/A
Control Device
None
Flare
By-product butadiene dimer
recovery
None
Boiler
None
Boiler
Boiler
None
Abatement collection system
for waste liquids and vapors
routed to a boiler
Boiler
None
None
None
Control
Efficiency
0
98
100
0
99.9
0
99.9
99.9
0
99.9
99.9
0
0
0
-------
I ABU- C-24 CONTINUED
Chemical
Produced
Sulfolane
Sulfolane
Company
Facility H
Facility A
Vent Location
Reactant recycle accumulator
Light ends stripper
Caustic scrubber
Sulfolene flakes caustic scrubber
Sulfolane reactor
Uncontrolled
Emissions
tons/yr (Mg/yr)
1.73 (1.57)
7.57 (6.87)
99 (90)
32.3 (29.3)
0
Controlled
Emissions
tons/yr (Mg/yr)
0.034(0.031)
0.15 (0.14)
N/A
N/A
N/A
Control Device
Flare
Flare
None
None
None
Control
Efficiency
(%)
98
98
0
0
0
Sources: References 5, 8, and 9.
O
-------
TABLE C-25. BUTADIENE EMISSIONS FROM EQUIPMENT LEAKS ASSOCIATED WITH
MISCELLANEOUS USES OF BUTADIENE 5,8,9
Chemical Produced
Butadiene cylinders
Butadiene dimers
Butadiene-furfural cotrimer
Butadiene-vinylpyridine latex
1,4-Hexadiene
Dodecanedioic acid
O
oj Methyl methacrylate-butadiene-
10 styrene resins
Company
Facility A
Facility B
Facility A
Facility C
Facility D
Facility E
Facility F
Facility G
Uncontrolled
Emissions
lons/yr (Mg/yr)
<0. 1 (<0. 1)
4.3" (3.9)"
0.61 (0.5)c
Unknown
67.7u(6l.4)d
5.7 (5.2)
4.0 (3.6)
17.4(15.8)
Controlled
Emissions
tons/yr (Mg/yr)
N/A
—
—
0.61 (0.55)
59.3 (53.8)
—
—
—
Controls
None
Ambient monitoring,"1 double mechanical
seals
Rupture discs
Quarterly LDAR, some rupture discs
Some double mechanical seals, some
rupture discs, some closed sampling
Visual inspections'
Unknown
Ambient monitoring1*
Control
Efficiency
0
0, 100
100
32, 100
e
0
...
0
-------
n
u>
u>
TABLE C-25 CONTINUED
Chemical Produced
Sulfolane
Tetrahydrophthalic
anhydride/acid
Comparo
Facility A
Facility H
Facility I
Uncontrolled
Emissions
tons/yr (Mg/yr)
14.7 (13.3)
1.8 (1.6)
2.4 (2.2)
Controlled
Emissions
tons/yr (Mg/yr)
N/A
N/A
—
Controls
None
None
Visual inspectionsf
Control
Efficiency
(%)
0
0
0
Source: References 5, 8, and 9.
"Excludes pumps with double mechanical seals.
bAmbient monitoring in the vicinity was being used to detect elevated VOC levels, a potential indication of equipment leaks.
'Excludes pressure relief devices since all are controlled.
''Excludes pumps with double mechanical seals and closed sampling ports.
'Each control is 100-percent effective; however, not all components are controlled, so overall reduction is not equal to 100 percent.
"For visual inspections, no reduction was given due to inadequate information.
"—" means no data available.
LDAR = leak detection and repair program.
-------
REFERENCES FOR APPENDIX C
1. Memorandum from K. Q. Kuhn and R. A. Wassel, Radian Corporation, to
the Butadiene Source Category Concurrence File, March 25, 1986. "Estimate of
1,3-Butadiene Emissions from Production Facilities and Emissions Reductions
Achievable with Additional Controls."
2. Memorandum from R. A. Wassel and K. Q. Kuhn, Radian Corporation, to the
Butadiene Source Category Concurrence File, April 8, 1986. "Estimates of
1,3-Butadiene Emissions from Styrene-Butadiene Copolymer Facilities and Emissions
Reductions Achievable with Additional Controls."
3. Randall, J. L. et al., April 1989. Fugitive Emissions from the 1,3-Butadiene
Production Industry: A Field Study, Final Report. Radian Corporation. Prepared for
the 1,3-Butadiene Panel of the Chemical Manufacturers Association, p. 5-11.
4. Memorandum from E. P. Epner, Radian Corporation, to the Butadiene Source
Category Concurrence File, March 27, 1986. "Estimates of 1,3-Butadiene from
Polybutadiene Facilities and Emissions Reductions Achievable with Additional
Controls."
5. Memorandum from K. Q. Kuhn and R. C. Burt, Radian Corporation, to the Butadiene
Source Category Concurrence File, December 12, 1986. "Estimates of 1,3-Butadiene
Emissions from Miscellaneous Sources and Emissions Reductions Achievable with
Candidate NESHAP Controls."
6 Memorandum from E. P. Epner, Radian Corporation, to L. B. Evans, U.S.
Environmental Protection Agency, Chemicals and Petroleum Branch, December 23,
1985 "Estimates of 1,3-Butadiene Emissions from Neoprene Facilities and Emissions
Reductions Achievable with Additional Controls."
7 Memorandum from R. Burt and R. Howie, Radian Corporation, to L. B. Evans, U.S.
Environmental Protection Agency, Chemicals and Petroleum Branch, January 29, 1986.
"Estimates of Acrylonitrile, Butadiene, and Other VOC Emissions and Controls for
ABS and NBR Facilities."
C-34
-------
APPENDIX D
ESTIMATION METHODS FOR EQUIPMENT LEAKS
-------
APPENDIX D
ESTIMATION METHODS FOR EQUIPMENT LEAKS
An estimate of equipment leak emissions of butadiene depends on the
equipment type (e.g., pump seals, flanges, valves, etc.), the associated emission factor, and the
number of process components. For batch processes, the hours per year that butadiene
actually flows through the component is estimated from the reported percent of the year the
equipment operates. For continuous processes, butadiene is assumed to flow through the
equipment 8,760 hours per year.
In 1988 and 1989, the Chemical Manufacturer's Association established a panel
to study butadiene emissions from equipment leaks. Out of this study, the panel produced
average butadiene emission rates (see Table 4-7). These emission rates represent a range of
controls at the facility in the study, thus they cannot be used to calculate uncontrolled
emissions. For butadiene producers and major users of butadiene, these emission rates can be
used to calculate emissions where the number of equipment components and time in service is
known The estimate for each component type is the product of the emission rate, the
number of components, and the time in service.
component-specific
emission rate,
Ib/hr/component
no. of equipment
components in
butadiene service
no. of hrs/yr
in butadiene
service
The estimate for all equipment leaks is the sum of the total for each component type.
D-l
-------
Where an uncontroHed estimate is of interest, EPA methods have been
published in Protocol for Equipment Leak Emission Estimates.1 These include.
• an average emission factor approach;
• a screening ranges approach;
• an EPA correlation approach; and
• a unit-specific correlation approach.
The approaches differ in complexity; however, greater complexity usually yields more
accurate emissions estimates.
The simplest method, the average emission factor approach, requires that the
number of each component type be known. For each component, the type of service (gas,
light or heavy liquid), the butadiene content of the stream, and the time the component is in
service are needed. This information is then multiplied by the EPA's average emission
factors. Emission factors for SOCMI process units and refineries are shown in Tables D-l
and D-2 Emission factors for marketing terminals and oil and gas production are also
provided in the document. However, these are not provided here as no data on butadiene
from these industries were identified. This method is an improvement on using generic
emissions developed from source test data, inventory data, and/or engineering judgement.
However, this method should only be used if no other data are available because it may result
m an overestimation of actual equipment leak emissions. For each component, estimated
emissions are calculated as follows:
No. of
equipment
components
X
Weight %
butadiene
in the stream
X
Component-
specific
emission factor
No. of hrs/yr in
butadiene service
D-2
-------
TABLE D-l. SOCMI AVERAGE TOTAL ORGANIC COMPOUND EMISSION FACTORS
FOR EQUIPMENT LEAKS
Equipment Type
Valves '
Pump seals0
Compressor seals
Pressure relief valves
Connectors
Open-ended lines
Sampling connections
Service
Gas
Light liquid
Heavy liquid
Light liquid
Heavy liquid
Gas
Gas
All
All
All
Emission Factor*1"
Ib/hr/source (kg/hr/source)
0.01313 (0.00597)
0.00887 (0.00403)
0.00051 (0.00023)
0.0438 (0.0199)
0.01896 (0.00862)
0.502 (0.228)
0.229 (0.104)
0.00403 (0.00183)
0.0037 (0.0017)
0.0330 (0.0150)
Source: Reference 1.
a The emission factors presented in this table for gas valves, light liquid valves, light liquid pumps, and connectors
are revised SOCMI average emission factors.
h These factors are for total organic compound emission rates.
c The light liquid pump seal factor can be used to estimate the leak rate from agitator seals.
To obtain more accurate equipment leak emission estimates, one of the more
complex estimation approaches should be used. These approaches require that some level of
emissions measurement for the facility's equipment components be collected. These are
described briefly, and the reader is referred to the EPA protocol document for the calculation
details
The screening ranges approach (formerly known as the leak/no leak approach)
is based on a determination of the number of leaking and non-leaking components. This
approach may be applied when screening data are available as either "greater than or equal to
10,000 ppmv" or as "less than 10,000 ppmv." Emission factors for SOCMI facilities for these
two ranges of screening values are presented in Table D-3; Table D-4 contains emission
D-3
-------
TABLE D-2. REFINERY AVERAGE EMISSION FACTORS
Equipment type
Valves
Pump sealsb
Compressor seals
Pressure relief valves
Connectors
Open-ended lines
Sampling connections
Service
Gas
Light Liquid
Heavy Liquid
Light Liquid
Heavy Liquid
Gas
Gas
All
All
All
Emission Factor
(kg/hr/source)a
0.0268
0.0109
0.00023
0.114
0.021
0.636
0.16
0.00025
0.0023
0.0150
Source: Reference 1.
a These factors are for non-methane organic compound emission rates.
b The light liquid pump seal factor can be used to estimate the leak rate from agitator seals.
factors for refineries. Emission factors for marketing terminals and oil and gas production are
also available from Reference 1; however, as noted above, no data on whether these industries
are emission sources are available.
The EPA correlation approach offers an additional refinement to estimating
equipment leak emissions by providing an equation to predict mass emission rate as a
function of screening value for a specific equipment type. Correlation equations for SOCMI
process units and for petroleum process units are provided in Reference 1, along with their
respective correlation curves. The EPA correlation approach is preferred when actual
screening values are available.1
The unit-specific correlation approach requires the facility to develop its own
correlation equations and requires more rigorous testing, bagging, and analyzing of equipment
leaks to determine mass emission rates.
D-4
-------
TABLE D-3 SOCMI SCREENING VALUE RANGE TOTAL ORGANIC COMPOUND EMISSION FACTORS
FOR EQUIPMENT LEAK EMISSIONS"
> 10,000 ppmv Emission Factor6
Source: Reference 1.
< 10,000 ppmv Emission Factor1"
Equipment Type
Valves
Pump seals0
Compressor seals
Pressure relief valves
Connectors
Open-ended lines
Service
Gas
Light liquid
Heavy liquid
Light liquid
Heavy liquid
Gas
Gas
All
All
lb/hr/source(kg/hr/source)
0.1720(0.0782)
0.1962 (0.0892)
0.00051 (0.00023)
0.535 (0.243)
0.475 (0.216)
3.538 (1.608)
3.720 (1.691)
0.249(0.113)
0.02629(0.01195)
lb/hr/source(kg/hr/source)
0.000288(0.000131)
0.000363 (0.000165)
0.00051 (0.00023)
0.00411 (0.00187)
0.00462 (0.00210)
0.1967 (0.0894)
0.0983 (0.0447)
0.0001782 (0.0000810)
0.00330(0.00150)
The emission factors presented in this table for gas valves, light liquid valves, light liquid pumps, and connectors are revised SOCM> 10,000/<
10,000 ppmv emission factors.
These factors are for total organic compound emission rates.
The light liquid pump seal factors can be applied to estimate the leak rate from agitator seals.
-------
TABLE D-4. REFINERY SCREENING RANGES EMISSION FACTORS
Equipment Type
Valves
Pump seals'5
Compressor seals
Pressure relief valves
Connectors
Open-ended lines
Service
Gas
Light Liquid
Heavy Liquid
Light Liquid
Heavy Liquid
Gas
Gas
All
All
> 10,000 ppmv
Emission Factor
(kg/hr/source)a
0.2626
0.0852
0.00023
0.437
0.3885
1.608
1.691
0.0375
0.01195
<1 0,000 ppmv
Emission Factor
(kg/hr/source)a
0.0006
0.0017
0.00023
0.0120
0.0135
0.0894
0.0447
0.00006
0.00150
Source: Reference 1.
a These factors are for non-methane organic compound emission rates.
b The light liquid pump seal factors can be applied to estimate the leak rate from agitator seals.
Appendix A of the EPA protocol document provides example calculations for
each of the approaches described above.
Adjusting any of the estimates derived from the EPA approaches requires that
facility control practices be known. Table 4-9 presents control techniques and typical
efficiencies by equipment component that may be applied to emission estimates for each
component type.
D-6
-------
REFERENCES FOR APPENDIX D
1. U.S. EPA. Protocol for Equipment Leak Emission Estimates. EPA-453/R-95-017. Research
Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, 1995. p. 2-10.
D-7
-------
APPENDIX E
SUMMARY OF 1992 TRI AIR EMISSIONS DATA FOR 1,3-BUTADIENE
-------
TABLE E-l SUMMARY OF 1992 TRI AIR EMISSIONS DATA FOR 1,3-BUTADIENE
SIC1
NA
No
28
2046
2369
2621
2641
2812
2812
2812
2819
2821
2821
2821
2821
2821
2821
2821
2821
2821
2821
2821
2821
2821
2821
SIC2
data
2819
NA
2821
2672
2821
2813
2821
2821
2821
2822
NA
NA
2869
2869
NA
NA
2869
2822
NA
2869
2869
SIC3
2821
NA
2821
3479
2819
2869
2869
2869
NA
NA
NA
NA
2865
NA
2813
SIC4
2834
3081
NA
2821
NA
NA
NA
NA
NA
SIC5
2869
NA
2822
SIC6
2979
2865
Facility Name
Goodyear Tire & Rubber Co. Plant 5
Rohm & Haas Kentucky Inc
Dow Chemical USA Midland Site
Penford Prods. Co.
Texas Eastman Company
W.R Grace & Co.
Nashua Corp. Computer Products Div.
Dow Chemical Co Texas Operations
Dow Chemical Co. Louisiana Div.
BF Goodrich BFG Intermediates Co. Inc.
Elf Atochem N.A. Inc
BASF Corp.
GE Chemicals Inc.
Reichhold Chemicals Inc.
Rexene Corp. Polypropylene Plant
Phillips Petroleum Co. Houston Chemical
Complex
Goodyear Tire & Rubber Co.
GE Chemicals Inc. Chemicals
Union Carbide Chemicals & Plastics Co.
Texas City Plant
Uniroyal Chemical Co. Inc.
Reichhold Chemicals Inc.
Quantum Chemical Corp. USI Div.
Kaneka Texas Corp
Rohm & Haas Unocal Chemical Division
Quantum Chemical Corp. La Porte
City
Akron
Louisville
Midland
Cedar Rapids
Longview
Owensboro
Merrimack
Freeport
Plaquemine
Calvert City
Axis
Chattanooga
Washington
Cheswold
Odessa
Pasadena
Calhoun
Ottawa
Texas City
Painesville
Chickamauga
Clinton
Pasadena
Charlotte
La Porte
State
OH
KY
Ml
IA
TX
KY
NH
TX
LA
KY
AL
TN
WV
DE
TX
TX
GA
IL
TX
OH
GA
IA
TX
NC
TX
Point Air
Release
(Ib/yr)'
324
2,300
5,720
250
49,000
115,300
36
52,000
41,000
170
12,886
150,000
20,000
64,688
10,766
11,000
12,332
12,100
19,696
3,066
8,100
6,900
3,200
6,470
5,744
Non-point
Air Release
(Ib/yr)1
3,500
8,600
14,009
250
11,000
18,500
36
46,000
12,000
5,100
2,325
1,600
60,000
5,383
34,479
26,000
19,552
18,513
10,409
14,452
8,900
9,800
12,000
6,140
5,380
Total
(Ib/yr)1
3,824
10,900
19,729
500
60,000
133,800
72
98,000
53,000
5,270
15,211
151,600
80,000
70,071
45,245
37,000
31,884
30,613
30,105
17,518
17,000
16,700
15,200
12,610
11,124
Notes
Assumed SIC Code 28
2979 is an invalid code
Point and non-point are avgs"
2672 is an invalid code
-------
TABLE E-l. CONTINUED
SIC1
2821
2821
2821
2821
2821
2821
2821
2821
2821
2821
2822
2822
2822
2822
2822
2822
2822
2822
2822
2822
2822
2822
2822
2822
SIC2
2869
3086
NA
3086
3086
2899
NA
2869
2822
NA
NA
NA
2869
NA
2821
2821
2865
2865
NA
3087
SIC3
NA
NA
NA
NA
2822
NA
2869
NA
2869
SIC4
NA
NA
2873
SIC5
SIC6
Facility Name
Quantum Chemical Corp USI Div.
Monsanto Co
Goodyear Tire & Rubber Co. Akron Polymer
Plant
Dow Chemical Dalton Site
Dow North America Allyn's Point Plant
Rhone-Poulenc Inc. Walsh Div.
Ricon Resins Inc.
Amoco Chemical Co.
Rohm & Haas Delaware Valley Inc.
Rohm & Haas Delaware Valley Inc.
Miles Inc. Polysar Rubber Div.
Firestone Synthetic Rubber & Latex Co.
Ameripol Synpol Corporation
Goodyear Tire & Rubber Co. Houston
Chemical Plant
Du Pont Pontchartrain Works
Zeon Chemicals Kentucky Inc.
Goodyear Tire & Rubber Co. Beaumont
Chemical Plant
BASF Corp.
Miles Inc.
Firestone Synthetic Rubber & Latex Co.
Dynagen Inc. of General Tire Inc.
Du Pont Beaumont Plant Beaumont Works
American Synthetic Rubber Corp.
Shell Chemical Co.
City
Morris
Addyston
Akron
Dalton
Gales Ferry
Gastonia
Grand
Junction
Whiting
Kankakee
La Mirada
Orange
Orange
Port Neches
Houston
La Place
Louisville
Beaumont
Monaca
Houston
Lake Charles
Odessa
Beaumont
Louisville
Belpre
State
IL
OH
OH
GA
CT
NC
CO
IN
IL
CA
TX
TX
TX
TX
LA
KY
TX
PA
TX
LA
TX
TX
KY
OH
Point Air
Release
(Ib/yr)1
3,000
6,000
892
40
45
242
750
250
120
0
4,400
7,000
2,300
9,000
56,000
26,841
6,600
38,000
14,300
4,000
11,150
8,997
0
2,300
Non-point
Air Release
(Ib/yr)1
7,200
860
2,979
1,800
1,340
807
250
750
300
242
350,000
93,000
81,500
60,724
5,200
33,844
42,000
17
15,600
24,540
15,222
6,568
14,000
8,400
Total
(Ib/yr)1
10,200
6,860
3,871
1,840
1,385
1,049
1,000
1,000
420
242
354,400
100,000
83,800
69,724
61,200
60,685
48,600
38,017
29,900
28,540
26,372
15,565
14,000
10,700
Notes
Point and non-point are avgsb
Point and non-point are avgsb
-------
TABLE E-l CONTINUED
SIC1
2822
2822
2822
2822
2822
2865
2865
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
SIC2
NA
2891
NA
NA
NA
2821
NA
NA
NA
NA
2865
2821
2822
NA
2865
NA
SIC3
NA
2822
NA
2821
2819
SIC4
NA
SIC5
SIC6
Facility Name
Copolymer Rubber & Chemical Corp.
Gencorp Polymer Prods Latex
BASF Corp.
Enichem Elastomers Americas Inc.
Firestone Synthetic Rubber & Latex Co.
Buffalo Color Corp
Amoco Chemical Co. Plant B
Lyondell Petrochemical Co.
Texas Petrochemicals Corporation
Occidental Chemical Corp.
Amoco Chemical Co Chocolate Bayou Plant
Texaco Chemical Co.
Exxon Chemical Co. Baton Rouge Chemical
Plant
Phillips 66 Co. Philtex/Ryton Complex
BF Goodrich Co. Akron Chemical Plant
Union Carbide Chemicals & Plastics Co.
Institute WV Plant Ops.
Oxy Petrochemical Inc. Corpus Christi Plant
Exxon Chemical Co. Baytown Olefins Plant
Union Carbide Chemicals & Plastics Co
Seadrift Plant
Mobil Chemical Co. Olefins/Aromatics Plant
Du Pont Sabine River Works
Texaco Chemical Co Port Arthur Chemical
Plant
Union Texas Prods. Corp. Geismar Ethylene
Plant
City
Baton Rouge
Mogadore
Chattanooga
Baytown
Akron
Buffalo
Texas City
Channelview
Houston
Alvin
Alvin
Port Neches
Baton Rouge
Borger
Akron
Institute
Corpus
Christi
Baytown
Port Lavaca
Beaumont
Orange
Port Arthur
Geismar
State
LA
OH
TN
TX
OH
NY
TX.
TX
TX
TX
TX
TX
LA
TX
OH
WV
TX
TX
TX
TX
TX
TX
LA
Point Air
Release
(Ib/yr)'
.500
650
150
250
39
1,800
14
245,000
37,240
13,000
250
15,000
5,900
33,000
25,000
15,751
26,300
15,000
12,929
2,547
26,522
12,000
1,300
Non-point
Air Release
(Ib/yr)1
10,000
5,000
750
250
117
36,000
173
61,000
125,710
95,400
102,000
55,000
55,000
25,000
21,000
20,61 1
9,700
19,000
20,965
29,005
3,428
8,300
14,600
Total
(Ib/yr)1
10,500
5,650
900
500
156
37,800
187
306,000
162,950
108,400
102,250
70,000
60,900
58,000
.46,000
36,362
36,000
34,000
33,894
31,552
29,950
20,300
15,900
Notes
Non-point is avg"
Point and non-point are avgsb
Point Is avg"
-------
TABLE E-l CONTINUED
SIC1
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2869
2879
2879
2879
2891
2899
2911
2911
SIC2
NA
NA
4463
2865
2821
NA
NA
NA
2821
2821
2879
2821
NA
2821
NA
2822
3081
NA
2869
SIC3
NA
2819
2895
2822
3083
NA
2869
NA
2822
NA
SIC4
NA
NA
2087
NA
NA
SIC5
2821
SIC6
Facility Name
Du Pont Victoria Plant
Oxy Petrochemicals Inc
Mobil Chemical Corp
Union Carbide Chemicals & Plastics Co.
Marine Terminal
Vista Chemical Co. Lake Charles Chemical
Complex
Chevron Chemical Co
Lubrizol Petroleum Chemicals Co.
Lindau Chemicals Inc.
Hoescht-Celanese Corp. Pampa Plant
Westlake Petrochemicals Corp.
Exxon Chemical Americas Baytown
Chemical Plant
Union Carbide Corp. Indl. Chemicals
Morton Intl. Inc. MPM
Phillips Research Center
Sea Lion Tech. Inc.
Dixie Chemical Co. Inc.
Lubrizol Corp. Deer Park Plant
Monsanto Co.
Zeneca Inc. Perry Plant
Dow Chemical Co
Roberts Consolidated Ind. Inc.
3M
Chevron USA Products Co Port Arthur
Refinery
Shell Norco Manufacturing Complex E. Site
City
Victoria
Sulphur
Houston
Texas City
Westlake
Baytowm
Painesville
Columbia
Pampa
Sulphur
Baytown
Hahnville
Moss Point
Bartlesville
Texas City
Pasadena
Deer Park
Muscatine
Perry
Pittsburg
Mexico
Decatur
Port Arthur
Norco
State
TX
LA
TX
TX
LA
TX
OH
SC
TX
LA
TX
LA
MS
OK
TX
TX
TX
IA
OH
CA
MO
AL
TX
LA
Point Air
Release
(Ib/yr)'
10,,158
90
5,000
9,905
2,980
0
3,922
4,200
1,600
1,033
87
105
250
24
250
0
0
160,000
9,800
310
250
1,400
14,000
3,200
Non-point
Air Release
(Ib/yr)'
5,250
14,073
5,500
0
5,475
6.159
853
250
0
83
810
507
250
243
5
15
5
4,000
80
1,500
0
740
120,000
92,000
Total
(Ib/yr)'
15,408
14,163
10,500
9,905
8,455
6,159
4,775
4,450
1,600
1,116
897
612
, 500
267
255
15
5
164,000
9,880
1,810
250
2,140
134,000
95,200
Notes
Non-point Is avgb
Point and non-point are avgsb
Point and non-point are avgsb
Non-point Is avgb
Point is avg"
-------
TABLE E-l CONTINUED
SIC1
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
SIC2
2869
NA
NA
NA
2951
NA
NA
NA
2869
NA
5171
NA
NA
2819
NA
NA
NA
NA
NA
5171
NA
2819
2999
SIC3
2865
2992
NA
NA
2869
NA
NA
NA
SIC4
2821
NA
NA
SIC5
SIC6
Facility Name
Shell Oil Co Deer Park Mfg Complex
Texaco Refining & Marketing Inc. Puget
Sound Plant
Ashland Petroleum Co. St Paul Park
Refinery
Mobil Oil Beaumont Refinery
Star Ent. Inc. Delaware City Refinery
Amoco Oil Co. Whiting Refinery
Hess Oil Virgin Islands Corp (HOVIC)
Arco Cherry Point Refinery
Kerr-McGee Refining Corp.
Phillips 66 Co.
Star Ent. Inc. Port Arthur Plant
Exxon Baytown Refinery
Ashland Petroleum Co. Canton Refinery
Conoco Lake Charles Refinery
Citgo Petroleum Corp.
Conoco Billings Refinery
Ultramar Inc.
Marathon Oil Co.
Lion Oil Co.
Exxon Co. USA Benicia Refinery
Exxon Baton Rouge Refinery
BP Oil Co. Toledo Refinery
Phillips 66 Co.
Conoco Ponca City Refinery
City
Deer Park
Anacortes
Saint Paul
Park
Beaumont
Delaware City
Whiting
Kingshill
Femdale
Wynnewood
Sweeny
Port Arthur
Baytown
Canton
Westlake
Lake Charles
Billings
Wilmington
Texas City
El Dorado
Benicia
Baton Rouge
Oregon
Borger
Ponca City
State
TX
WA
MN
TX
DE
IN
VI
WA
OK
TX
TX
TX
OH
LA
LA
MT
CA
TX
AR
CA
LA
OH
TX
OK
Point Air
Release
(Ib/yr)'
10.960
23,000
17,046
13,000
0
0
0
0
320
0
2,803
2,580
256
130
31
27
270
830
0
580
440
210
18
510
Non-point
Air Release
(Ib/yr)1
57,679
10,000
0 .
1,300
13,000
8,600
7,394
6,900
3,900
3,402
9
174
2,162
1,500
1,500
1,400
750
180
1,006
400
460
690
870
350
Total
(Ib/yr)'
68,639
33,000
17,046
14,300
13,000
8,600
7,394
6,900
4,220
3,402
2,812
2,754
2,418
1,630
1,531
1,427
1,020
1,010
1,006
980
900
900
888
860
Notes
Non-point is avg"
m
Ui
-------
TABLE E-l CONTINUED
SIC1
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
SIC2
NA
NA
NA
NA
2951
NA
NA
5171
NA
NA
2869
NA
NA
NA
NA
NA
2869
NA
4613
NA
SIC3
NA
NA
2873
2992
NA
SIC4
NA
NA
SIC5
SIC6
-
Facility Name
Chevron USA Products Co Hawaiian
Refinery
Mobil Joliet Refinery Corp.
Texaco Refining & Marketing Inc. Lap
Ashland Petroleum Co. Catlettsburg Refinery
Chevron USA Inc. El Paso Refinery
Shell Oil Co. Anacortes Refinery
Cenex Refinery
Southwestern Refining Co. Inc.
Crown Central Petroleum Corp. Houston
Refinery
Exxon Billings Refinery
Amerada Hess Corp.
Amoco Oil Co.
Chevron Products Co. Pascagoula Refinery
Phibro Refining Krotz Springs
Conoco Denver Refinery
Amoco Oil Co. Texas City Refinery
Chevron USA Products Co. El Segundo
Refinery
Chevron USA Products Co.
Fletcher Oil & Refining Co.
Lyondell Petrochemical Co. Houston Refinery
Mobil Oil Paulsboro Refinery
Total Petroleum Inc. Alma Refinery
Arco Prods. Co. LA Refinery
City
Kapolei
Joliet
Wilmington
Catlettsburg
El Paso
Anacortes
Laurel
Corpus
Christi
Pasadena
Billings
Purvis
Mandan
Pascagoula
Krotz Springs
Commerce
City
Texas City
El Segundo
Philadelphia
Carson
Houston
Paulsboro
Alma
Carson
State
HI
IL
CA
KY
TX
WA
MT
TX
TX
MT
MS
NO
MS
LA
CO
TX
CA
PA
CA
TX
NJ
Ml
CA
Point Air
Release
(Ib/yr)'
. 5
350
0
455
400
2
250
250
5
0
0
0
0
90
0
0
0
0
250
0
0
0
4
Non-point
Air Release
(Ib/yr)'
750
200
540
70
110
500
250
250
482
460
415
410
390
242
320
310
310
301
5
250
250
250
240
Total
(Ib/yr)'
755
550
540
525
510
502
500
500
487
460
415
410
390
332
320
310
310
301
255
250
250
250
244
Notes
Point and non-point are avgs"
Point and non-point are avgsb
Point and non-point are avgsb
Point and non-point are avgsb
Non-point is avgb
Non-point is avg"
Non-point is avg"
-------
TABLE E-l CONTINUED
SIC1
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
2911
SIC2
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
5171
2869
5171
NA
NA
NA
NA
NA
NA
NA
SIC3
NA
SIC4
SIC5
SIC6
Facility Name
Shell Oil Co Wood River Mfg Complex
Phibro Energy USA Inc
Tosco Refining Co.
Total Petroleum Inc.
Mobil Oil Corp. Chalmette Refinery
Valero Refining Co.
Sun Refining & Marketing Co.
Giant Refining Co Ciniza
Texaco Refining & Marketing Inc
Diamond Shamrock Refining & Marketing
Co. Three Rivers
BP Oil Co. Ferndale Refinery
Exxon Eastside Chemical Plant
Texaco Refining & Marketing Inc.
Exxon Refining & Marketing Terminal
Sun Refining & Marketing Co.
Chevron USA Products Co Richmond
Refinery
Sun Refining & Marketing Co.
Phibro Energy USA Inc
Fina Oil & Chemical Co.
Mobil Oil Corp Torrence Refinery
Texaco Refining & Marketing Inc.
Marathon Oil Co.
Unocal Corp. Carson Plant
Uno-Ven Co. Chicago Refinery
City
Roxana
Texas City
Martinez
Ardmore
Chalmette
Corpus
Christ!
Marcus Hook
Jamestown
Bakersfield
Three Rivers
Ferndale
Linden
El Dorado
Linden
Oregon
Richmond
Philadelphia
Houston
Port Arthur
Torrence
Bakersfield
Detroit
Carson
Lemont
State
IL
TX
CA
OK
LA
TX
PA
NM
CA
TX
WA
NJ
KS
NJ
OH
CA
PA
TX
TX
CA
CA
Ml
CA
IL
Point Air
Release
(Ib/yr)1
. 0
171
17
0
9
98
0
100
80
0
51
34
0
0
0
0
0
7
0
16
9
0
1
0
Non-point
Air Release
(Ib/yr)1
230
58
200
150
140
38
120
10
29
100
46
63
91
88
77
74
58
49
42
15
22
22
20
19
Total
(Ib/yr)'
230
229
217
150
149
136
120
110
109
100
97
97
91
88
77
74
58
56
42
31
31
22
21
19
Notes
-------
TABLE E-l. CONTINUED
SIC1
2911
2911
2911
2911
2911
3312
3579
8731
SIC2
NA
NA
NA
2819
NA
NA
NA
8711
SIC3
2869
8734
SIC4
NA
NA
SIC5
SIC6
Facility Name
Marathon Oil Co Louisiana Refinery
Sun Refining & Marketing Co
Countrymark Cooperative Inc. Assn. Inc. Mt.
Vernon Refinery
Shell Oil Co. Martinez Mfg. Complex
Star Ent. Inc. PAAC
Bethlehem Steel Corp. Burns Harbor Div.
Xerox
Chevron Research & Technology Co.
City
Garyville
Tulsa
Mount Vernon
Martinez
Port Neches
Burns Harbor
Oklahoma
City
Richmond
State
LA
OK
IN
CA
TX
IN
OK
CA
Point Air
Release
(Ib/yr)'
, 5
0
0
0
1
0
4,200
1
Non-point
Air Release
(Ib/yr)'
12
8
5
2
0
250
0
0
Total
(Ib/yr)'
17
8
5
2
1
250
4,200
1
Notes
Point Is avgb
Non-point Is avg"
Non-point Is avg"
'Includes any controls in place at the facility.
bAir releases were given as a range. The data were averaged for the table.
-------
TECHNICAL REPORT DATA
(PLEASE READ INSTRUCTIONS ON THE REVERSE BEFORE COMPLETING)
1. REPORT NO.
3. RECIPIENTS ACCESSION NO.
4. TITLE AND SUBTITLE
Locating And Estimating Air Emissions From Sources Of 1,3-Butadiene
(EPA-454/R-96-008)
5. REPORT DATE
November 1996
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
I
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
"Eastern Research Group
Post Office Box 2010
Morrisville, NC 27560
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D2-0160
12. SPONSORING AGENCY NAME AND ADDRESS
US Environmental Protection Agency
OAQPS/EMAD/EFIG(MD-14)
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
FINAL
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA WORK ASSIGNMENT MANAGER: DENNIS BEAUREGARD (919) 541-5512
16. ABSTRACT
To assist groups interested in inventorying air emissions of various potentially toxic substances, the U.S.
Environmental Protection Agency is preparing a series or documents such as this to compile available
information on sources and emissions of these suhstances. This document deals specifically with
1,3-Butadiene. Its intended audience includes Federal, State and local air pollution personnel and others
interested in locating potential emitters of 1,3-Butadiene and in making gross estimates 01 air emissions
therelri'in.
This document presents information on (1) the types of sources that may emit 1,3-Butadiene, (2) process
variations and release points for these sources, and (3) available emissions information indicating the potential
for 1,3-ButaJiene releases into the air from each operation.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
1,3-BUTADIENE
AIR EMISSION SOURCES
TOXIC SUBSTANCES
EMISSION ESTIMATION
b. IDENTIFIERS/OPEN ENDED TERMS c. COSATI FIELD/GROUP
B. DISTRIBUTION STATEMENT
' UNLIMITED
UNCLASSIFIED
21. NO. OF PAGES
251
22. PRICE
UNCLASSIFIED
U.S. Environmental Protection Agency
------- |