EPA-454/R-93-044 LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF CHLOROBENZENES (REVISED) Office of Air Quality Planning and Standards U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711 March 1994 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. ii CONTENTS Section Page DISCLAIMER ..................................................... ii LIST OF FIGURES .................................................. vi LIST OF TABLES .................................................. vii 1.0 PURPOSE OF DOCUMENT ..................................... 1-1 1.1 Reference for Section 1.0 ................................... 1-5 2.0 OVERVIEW OF DOCUMENT CONTENTS .......................... 2-1 2.1 References for Section 2.0 .................................. 2-5 3.0 BACKGROUND .............................................. 3-1 3.1 Nature of Pollutant ....................................... 3-1 3.1.1 Properties of Chlorobenzenes ........................... 3-5 3.1.2 Properties of Monochlorobenzene ........................ 3-6 3.1.3 Properties of Dichlorobenzenes .......................... 3-6 3.1.4 Properties of Trichlorobenzenes ......................... 3-7 3.1.5 Properties of Hexachlorobenzene ........................ 3-7 3.2 Overview of Production and Use .............................. 3-8 3.3 References for Section 3.0 ................................. 3-16 4.0 EMISSIONS FROM CHLOROBENZENES PRODUCTION ............... 4-1 4.1 Equipment Leak Emissions .................................. 4-1 4.2 Monochlorobenzene Production ............................... 4-4 4.2.1 Process Description .................................. 4-4 4.2.2 Emissions ........................................ 4-9 4.3 Dichlorobenzenes Production ............................... 4-10 4.3.1 Ortho- and Para-Dichlorobenzene ....................... 4-11 4.3.2 Meta-Dichlorobenzene ............................... 4-13 4.3.3 Emissions ........................................ 4-14 4.4 Trichlorobenzenes Production ............................... 4-14 4.5 References for Section 4.0 ................................. 4-18 5.0 EMISSIONS FROM MAJOR USES OF CHLOROBENZENE .............. 5-1 5.1 Manufacture of Nitrochlorobenzenes from Monochlorobenzene ......... 5-1 5.1.1 Process Description .................................. 5-2 5.1.2 Emissions ......................................... 5-2 5.2 Manufacture of Diphenyl Oxide from Monochlorobenzene ............ 5-3 5.2.1 Process Description .................................. 5-4 5.2.2 Emissions ......................................... 5-4 5.3 Manufacture of Phenylphenols from Monochlorobenzene ............. 5-5 5.4 Manufacture of 4,4′-Dichlorodiphenylsulfone from Monochlorobenzene . 5-5 iii TABLE OF CONTENTS (continued) Section Page 5.4.1 Process Description .................................. 5-6 5.4.2 Emissions ......................................... 5-6 5.5 Manufacture of 3,4-Dichloroaniline from Ortho-Dichlorobenzene ....... 5-7 5.5.1 Process Description .................................. 5-7 5.5.2 Emissions ......................................... 5-9 5.6 Use of Para-Dichlorobenzene in the Production of Polyphenylene Sulfide ............................................... 5-10 5.6.1 Process Description ................................. 5-11 5.6.2 Emissions ........................................ 5-13 5.7 Use of Chlorobenzenes in the Manufacture of Toluene Diisocyanate .... 5-13 5.7.1 Process Description ................................. 5-14 5.7.2 Emissions ........................................ 5-17 5.8 Use of Chlorobenzenes in the Production of Dyes and Pigments ....... 5-17 5.8.1 Use of Chlorobenzenes in the Synthesis of Intermediates ....... 5-18 5.8.2 Use of Chlorobenzenes as Process Solvent ................. 5-20 5.9 Use of Monochlorobenzene and Ortho-Dichlorobenzene as Dye Carriers in Textile Dyeing ......................................... 5-30 5.10 Use of 1,2,4-Trichlorobenzene as a Dye Carrier in the TExtile Dyeing Industry .............................................. 5-31 5.11 Use of Para-Dichlorobenzene as a Pesticide ..................... 5-32 5.12 Use of 1,2,4-Trichlorobenzene in the Manufacture of the Herbicide Banvel® .............................................. 5-33 5.12.1 Process Descriptions ................................ 5-33 5.12.2 Emissions ........................................ 5-34 5.13 Use of Ortho-Dichlorobenzene as a Solvent in Pharmaceutical Manufacturing .......................................... 5-35 5.13.1 Process Description ................................. 5-35 5.13.2 Emissions ........................................ 5-37 5.14 Miscellaneous Uses of Chlorobenzenes ........................ 5-38 5.15 References for Section 5.0 ................................. 5-39 6.0 EMISSIONS FROM THE USE OF MATERIALS CONTAINING CHLOROBENZENES .......................................... 6-1 6.1 Use of para-Dichlorobenzene in Moth Control .................... 6-1 6.2 Use of para-Dichlorobenzene as a Space Deodorant ................ 6-2 6.2.1 Process Description .................................. 6-2 6.2.2 Emissions ......................................... 6-3 6.3 Use of Chlorobenzenes as Solvents in Organic Solvent Cleaning Operations ............................................. 6-3 6.3.1 Process Description .................................. 6-4 6.3.2 Emissions ......................................... 6-5 iv TABLE OF CONTENTS (continued) Section Page 6.4 Use of Trichlorobenzenes in Wood Preservatives .................. 6-6 6.5 References for Section 6.0 .................................. 6-7 7.0 BYPRODUCT EMISSIONS -- PROCESSES UNRELATED TO PRODUCTION OR USE OF CHLOROBENZENES ................................. 7-1 7.1 Volatilization of Chlorobenzenes from Wastewater Treatment Operations ............................................. 7-1 7.2 Hazardous and Solid Waste Incineration ........................ 7-3 7.3 Burning of Waste Oil ..................................... 7-6 7.4 Hexachlorobenzene Generation During Chlorinated Solvent Production . 7-6 7.4.1 Process Description .................................. 7-7 7.4.2 Emissions ......................................... 7-7 7.5 References for Section 7.0 ................................. 7-14 8.0 AMBIENT AIR AND STATIONARY SOURCE TEST PROCEDURES ....... 8-1 8.1 EPA Method TO-1 ....................................... 8-1 8.2 EPA Method TO-14 ...................................... 8-2 8.3 EPA Method 0030 ........................................ 8-5 8.4 EPA Method 5040 ........................................ 8-5 8.5 EPA Method 0010 ........................................ 8-8 8.6 EPA Method 8270 ....................................... 8-11 8.7 References for Section 8.0 ................................. 8-12 APPENDIX A POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES EMISSIONS .......................................A-1 APPENDIX B TEXTILE FIBER DYEING FACILITIES WITH ANNUAL SALES GREATER THAN $1 MILLION ........................B-1 APPENDIX C SUMMARY OF EMISSION FACTORS LISTED IN THIS DOCUMENT ......................................C-1 v FIGURES Number Page 3-1 End Uses of Monochlorobenzene .................................. 3-11 3-2 End Uses of o-Dichlorobenzene .................................. 3-12 3-3 End Uses of p-Dichlorobenzene .................................. 3-13 3-4 End Uses of Trichlorobenzene .................................... 3-14 4-1 Monochlorobenzene Continuous Production Process Diagram ............... 4-7 4-2 Dichlorobenzene and Trichlorobenzene Continuous Production Diagram ...... 4-12 5-1 Process Flow Diagram of Polyphenylene Sulfide Manufacture ............. 5-12 5-2 Basic Operations that may be Used in Toluene Diisocyanate Production ...... 5-16 5-3 Basic Operations that may be Used in Pharmaceutical Manufacturing ........ 5-36 7-1 Process Flow for the Production of Carbon Tetrachloride and Perchloroethylene by Hydrocarbon Chlorinolysis ..................................... 7-7 7-2 Process Flow Diagram for the Production of Perchloroethylene and Trichloroethylene by Chlorination .................................. 7-8 7-3 Process Flow Diagram for the Production of Perchloroethylene and Trichloroethylene by Oxychlorination ............................... 7-9 8-1 EPA Method TO-1 Sampling System ................................ 8-3 8-2 Tenax® Cartridge Design ........................................ 8-4 8-3 Canister Sampling System ....................................... 8-6 8-4 Schematic of Volatile Organic Sampling Train (VOST) ................... 8-7 8-5 Schematic Diagram of Trap Desorption/Analysis System .................. 8-9 8-6 Modified Method 5 Sampling Train ................................ 8-10 vi TABLES Number Page 3-1 Synonyms and Trade Names for Chlorobenzenes ........................ 3-2 3-2 Properties of Industrially Significant Chlorobenzenes ..................... 3-3 3-3 End Uses of Chlorobenzenes ..................................... 3-15 4-1 Average Emission Factors for Fugitive Equipment Leak Emissions .......... 4-3 4-2 Control Techniques and Efficiencies Applicable to Equipment Leak Emissions . 4-5 4-3 Chemical Producers of Monochlorobenzene - 1989 ...................... 4-9 4-4 Emission Factors for a Hypothetical Monochlorobenzene Production Plant ..... 4-10