LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF METHYLENE CHLORIDE Final Report Prepared for: Dallas Safriet Emission Inventory Branch U. S. Environmental Protection Agency Research Triangle Park, North Carolina 27711 Prepared by: Radian Corporation Post Office Box 13000 Research Triangle Park, North Carolina 27709 April 22, 1993 This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S. Environmental Protection Agency, and has been approved for publication. Any mention of trade names or commercial products is not intended to constitute endorsement or recommendation for use. EPA-454/R-93-006 TABLE OF CONTENTS Section Page 1 Purpose of Document ................... 1 References for Section 1 .............. 4 2 Overview of Document Contents .............. 5 3 Background ....................... 7 Nature of Pollutant ................ 7 Overview of Production and Use ........... 9 References for Section 3 .............. 13 4 Emissions from Methylene Chloride Production ...... 15 Process Descriptions ................ 15 Emission Sources and Controls ........... 20 Emission Estimates ................. 25 References for Section 4 .............. 36 5 Emissions from Uses of Methylene Chloride ........ 37 Paint Stripper Industry .............. 37 References for Paint Stripper Industry ....... 53 Plastics Manufacturing ............... 55 Polycarbonate Resins ..............55 Triacetate Fiber ................64 Plastics Production ..............68 References for Plastics Manufacturing ....... 72 Flexible Urethane Foam Production Industry ..... 73 References for Polyurethane Foam Industry ..... 81 Pharmaceutical Manufacturing ............ 83 References for Pharmaceutical Manufacturing .... 97 Solvent Cleaning and Photoresist Stripping ..... 99 References for Solvent Cleaning and Photoresist Stripping .................. 120 Aerosol Packaging and Dispensing .......... 121 ii TABLE OF CONTENTS (Continued) Section Page References for Aerosol Packaging and Dispensing . 132 Miscellaneous ................... 135 Pesticide Manufacturing ........... 135 Photographic Film Manufacture ........ 138 Paints and Coatings ............. 141 References for Miscellaneous Section ........ 143 6 Source Test Procedures ................. 145 EPA Method 0030 .................. 145 EPA Methods 5040 And 5041 ............. 147 EPA Method 18 ................... 149 Compendium Methods TO-1, TO-2, and TO-14 ...... 151 NIOSH Method 1005 ................. 153 References for Section 6 .............. 154 APPENDICES Appendix Page A Example Procedures to Estimate Methylene Chloride Emissions A-1 References for Appendix A ................ A-8 B National List of Paint Stripper Formulators (July 1987) . B-1 C National List of Aerosol Packagers ........... C-1 D TRIS List of Pharmaceutical Facilities Using Methylene Chloride ........................ D-1 E Calculation of Uncontrolled Open-Top Vapor Cleaner Emission Factor Incorporating Recycle .............. E-1 iii LIST OF TABLES Table Page 1 Chemical and Physical Properties of Methylene Chloride . 8 2 Estimated United States Methylene Chloride Consumption By End Use for 1991 [in Mg (Million Pounds)] ...........11 3 Potential Source Categories of Methylene Chloride Emissions 12 4 United States Methylene Chloride Production ........16 5 Control Techniques And Efficiencies Applicable to Equipment Leak Emissions ......................22 6 Waste and Wastewater Emission Control Techniques and Efficiencies .......................26 7 1983 Reported Controls and Control Efficiencies from Facilities Producing Methylene Chloride ...............27 8 Average Emission Factors for Equipment Leak Emissions . 32 9 Emission Factors for Methylene Chloride Production ....34 10 Methylene Chloride Consumption in 1987 by Paint Stripper Sector ..........................39 11 Control Techniques for Emissions of Chlorinated Solvents from Paint Stripper Formulators ................44 12 Estimated Methylene Chloride Emissions from Paint Stripper Formulators (1988) ....................46 13 Estimated Methylene Chloride Emissions From Automobile Manufacturing Facilities, 1987 ..............48 14 Estimated Methylene Chloride Emissions From Large-Scale Military Users of Paint Stripper, 1987 ..........50 15 Paint Stripping Emissions Factors .............51 16 Additional Control Techniques for Emissions of Methylene Chloride Solvents from Paint Stripper Users ........52 17 Estimated 1983 Emissions and Controls at Facilities Using Methylene Chloride in Polycarbonate Resin Production . 59 18 Estimated Methylene Chloride Emissions and Controls Associated with Triacetate Fiber Manufacture .............67 19 Estimated Methylene Chloride Emissions and Controls Associated with Plastics Production at General Electric, Pittsfield, Massachusetts in 1983 ...................69 20 Uncontrolled Emission Factors for Polyurethane Foam Production78 iv LIST OF TABLES (Continued) Table Page 21 Control Techniques and Efficiencies Used to Estimate Controlled Emissions from Polyurethane Flexible Foam Production ........................79 22 Partial List of Pharmaceutical Manufacturing Facilities that Use Methylene Chloride ..................84 23 Methylene Chloride Purchases and Ultimate Disposition by Pharmaceutical Manufacturers ..............91 24 Methylene Chloride Emission Factors for Pharmaceutical Manufacturing ...............92 25 Available Control Techniques for OTVC Operations .... 113 26 Available Control Techniques for In-Line Operations . 114 27 Available Control Techniques for Cold Cleaners ..... 115 28 Methylene Chloride Usage and Emission Factors for Uncontrolled and Controlled Cleaners ................. 117 29 National Emissions of MC From Organic Solvent Cleaners, (1987)118 30 Weight Percent of Methylene Chloride in Aerosol Product Tanks, Reported by Section 114 Questionnaire Respondents (1987) 123 31 Control Techniques for Emissions of Chlorinated Solvents from Aerosol Packagers (1988) ................ 129 32 Estimated Methylene Chloride Emissions from Aerosol Packagers in 1987 ......................... 131 33 Emissions from Three Points at a Pesticide Facility, 1988 137 v LIST OF FIGURES Figure Page 1 Locations of Plants Manufacturing Methylene Chloride . 17 2 Process Flow Diagram for the Production of Methylene Chloride and Co-products by the Direct Chlorination of Methane. 19 3 Process Flow Diagram for the Production of Methylene Chloride and Co-Products by the Hydrochlorination of Methanol . 21 4 Process Flow Diagram for the Production of Polycarbonate Resin .............................56 5 Process Flow Diagram for the Production of Triacetate Fibers 66 6 Schematic Flow Diagram of Polyurethane Flexible Foam Production. ........................76 7 Typical Synthetic Organic Pharmaceutical Chemical Process . 86 8 Pan Tablet Coating Process Solvent Recovery System ....94 9 Wurster Process Solvent Recovery System ..........96 10 Open Top Vapor Cleaner ................. 101 11 Cross-Rod Cleaner .................... 103 12 Monorail In-Line Cleaner ................ 105 13 Schematic Diagram of an In-Line Photoresist Stripping Machine106 14 Carburetor Cleaner ................... 108 15 Batch Cleaner Idling Emission Sources .......... 109 16 In-Line Cleaner Emission Sources ............ 110 17 Typical Aerosol Spray System .............. 125 18 Photographic Film Process with MC Emissions ....... 139 19 Schematic Diagram of Volatile Organic Sampling Train (VOST) 146 20 Schematic Diagram of Trap Desorption/Analysis System . 148 21 Integrated Bag Sampling Train .............. 150 vi SECTION 1 PURPOSE OF DOCUMENT The Environmental Protection Agency (EPA) and State and local air pollution control agencies are becoming increasingly aware of the presence of substances in the ambient air that may be toxic at certain concentrations. This awareness has led to attempts to identify source/receptor relationships and to develop control programs to regulate toxic emissions. Unfortunately, very little information is available on the ambient air concentrations of these substances or on the sources that may be discharging them to the atmosphere. To assist groups interested in inventorying air emissions of various potentially toxic substances, EPA is preparing a series of documents, such as this one, that compiles available information on sources and emissions. Existing documents in the series are listed below. Substance EPA Publication Number Acrylonitrile EPA-450/4-84-007a Carbon Tetrachloride EPA-450/4-84-007b Chloroform EPA-450/4-84-007c Ethylene Dichloride EPA-450/4-84-007d Formaldehyde (Revised) EPA-450/2-91-012 Nickel EPA-450/4-84-007f Chromium EPA-450/4-84-007g Manganese EPA-450/4-84-007h Phosgene EPA-450/4-84-007i Epichlorohydrin EPA-450/4-84-007j Vinylidene Chloride EPA-450/4-84-007k Ethylene Oxide EPA-450/4-84-007l Chlorobenzenes EPA-450/4-84-007m Polychlorinated Biphenyls (PCBs) EPA-450/4-84-007n Polycyclic Organic Matter (POM) EPA-450/4-84-007p Benzene EPA-450/4-84-007q Organic Liquid Storage Tanks EPA-450/4-88-004 Coal and Oil Combustion Sources EPA-450/2-89-001 Municipal Waste Combustors EPA-450/2-89-006 Perchloroethylene and EPA-450/2-90-013 1,3-Butadiene EPA-450/2-89-021 Chromium (supplement) EPA-450/2-89-002 Sewage Sludge EPA-450/2-90-009 Styrene EPA-450/4-91-029 1 This document deals specifically with methylene chloride (MC), also known as dichloromethane. The intended audience includes Federal, State and local air pollution personnel and others who are interested in locating potential emitters of MC and in making gross estimates