United States Office of Air Quality EPA-454/R-98-011 Environmental Protection Planning And Standards June 1998 Agency Research Triangle Park, NC 27711 AIR EPA LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF BENZENE Disclaimer 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 of use. EPA-454/R-98-011 ii TABLE OF CONTENTS Section Page LIST OF TABLES.....................................................x LIST OF FIGURES.................................................. xvi EXECUTIVE SUMMARY.............................................xx 1.0 PURPOSE OF DOCUMENT .......................................... 1-1 2.0 OVERVIEW OF DOCUMENT CONTENTS.............................. 2-1 3.0 BACKGROUND INFORMATION ...................................... 3-1 3.1 NATURE OF POLLUTANT..................................... 3-1 3.2 OVERVIEW OF PRODUCTION AND USE ......................... 3-4 3.3 OVERVIEW OF EMISSIONS.................................... 3-8 4.0 EMISSIONS FROM BENZENE PRODUCTION ........................... 4-1 4.1 CATALYTIC REFORMING/SEPARATION PROCESS................ 4-7 4.1.1 Process Description for Catalytic Reforming/Separation........... 4-7 4.1.2 Benzene Emissions from Catalytic Reforming/Separation .......... 4-9 4.2 TOLUENE DEALKYLATION AND TOLUENE DISPROPORTIONATION PROCESS ............................ 4-11 4.2.1 Toluene Dealkylation .................................... 4-12 4.2.2 Toluene Disproportionation ............................... 4-13 4.3 ETHYLENE PRODUCTION .................................... 4-16 4.3.1 Process Description ..................................... 4-16 4.3.2 Benzene Emissions from Ethylene Plants and Benzene Recovery from Pyrolysis Gasoline................................... 4-32 4.4 COKE OVEN AND COKE BY-PRODUCT RECOVERY PLANTS ...... 4-36 4.4.1 Process Description ..................................... 4-36 4.4.2 Benzene Emissions...................................... 4-46 iii TABLE OF CONTENTS, continued Section Page 4.5 METHODS FOR ESTIMATING BENZENE EMISSIONS FROM EMISSION SOURCES ........................................ 4-61 4.5.1 Process Vent Emissions, Controls, and Regulations..............4-62 4.5.2 Equipment Leak Emissions, Controls, and Regulations........... 4-70 4.5.3 Storage Tank Emissions, Controls, and Regulations ............. 4-77 4.5.4 Wastewater Collection and Treatment System Emissions, Controls, and Regulations................................. 4-82 4.5.5 Product Loading and Transport Operations Emissions, Controls, and Regulations ........................................ 4-85 5.0 EMISSIONS FROM MAJOR USES OF BENZENE......................... 5-1 5.1 ETHYLBENZENE AND STYRENE PRODUCTION .................. 5-2 5.1.1 Process Description for Ethylbenzene and Styrene Production Using Benzene Alkylation and Ethylbenzene Dehydrogenation ...... 5-3 5.1.2 Process Description for Ethylbenzene Production from Mixed Xylenes................................................ 5-9 5.1.3 Process Description for Styrene Production from Ethylbenzene Hydroperoxidation ...................................... 5-10 5.1.4 Process Description for Styrene Production by an Isothermal Process............................................... 5-12 5.1.5 Benzene Emissions from Ethylbenzene and Styrene Production via Alkylation and Dehydrogenation......................... 5-14 5.1.6 Control Technology for Ethylbenzene/Styrene Processes..........5-19 5.2 CYCLOHEXANE PRODUCTION ............................... 5-20 5.2.1 Process Description for Cyclohexane Production via Benzene Hydrogenation ......................................... 5-21 5.2.2 Benzene Emissions from Cyclohexane Production via Benzene Hydrogenation ......................................... 5-23 5.2.3 Process Description for Cyclohexane Production via Separation of Petroleum Fractions................................... 5-24 5.2.4 Benzene Emissions from Cyclohexane Production via Separation of Petroleum Fractions................................... 5-26 5.3 CUMENE PRODUCTION ..................................... 5-26 5.3.1 Process Descriptions for Cumene Production by Alkylating Benzene with Propylene.................................. 5-27 5.3.2 Benzene Emissions From Cumene Production.................. 5-34 iv TABLE OF CONTENTS, continued Section Page 5.4 PHENOL PRODUCTION ...................................... 5-35 5.4.1 Phenol Production Techniques ............................. 5-39 5.4.2 Benzene Emissions from Phenol Production ................... 5-47 5.5 NITROBENZENE PRODUCTION ............................... 5-49 5.5.1 Process Descriptions for Continuous Nitration ................. 5-49 5.5.2 Benzene Emissions from Nitrobenzene Production .............. 5-53 5.6 ANILINE PRODUCTION ...................................... 5-58 5.6.1 Process Descriptions for Aniline Production for Nitrobenzene ...... 5-58 5.6.2 Benzene Emissions from Aniline Production ................... 5-61 5.7 CHLOROBENZENE PRODUCTION ............................. 5-62 5.7.1 Process Description for Chlorobenzene Production by Direct Chlorination of Benzene.................................. 5-62 5.7.2 Benzene Emissions from Chlorobenzene Production............. 5-67 5.8 LINEAR ALKYLBENZENE PRODUCTION ....................... 5-70 5.8.1 Process Description for Production of LAB Using the Olefin Process............................................... 5-70 5.8.2 Benzene Emissions from LAB Production Using the Olefin Process............................................... 5-74 5.8.3 Process Description for Production of LAB Using the Chlorination Process..................................... 5-74 5.8.4 Benzene Emissions from LAB Production Using the Chlorination Process............................................... 5-78 5.9 OTHER ORGANIC CHEMICAL PRODUCTION .................... 5-80 5.9.1 Hydroquinone.......................................... 5-80 5.9.2 Benzophenone ......................................... 5-81 5.9.3 Benzene Sulfonic Acid ................................... 5-81 5.9.4 Resorcinol............................................. 5-81 5.9.5 Biphenyl.............................................. 5-82 5.9.6 Anthraquinone ......................................... 5-82 5.10 BENZENE USE AS A SOLVENT................................5-82 6.0 EMISSIONS FROM OTHER SOURCES................................. 6-1 6.1 OIL AND GAS WELLHEADS ................................... 6-1 v TABLE OF CONTENTS, continued Section Page 6.1.1 Description of Oil and Gas Wellheads......................... 6-1 6.1.2 Benzene Emissions from Oil and Gas Wellheads................. 6-2 6.2 GLYCOL DEHYDRATION UNITS ............................... 6-4 6.2.1 Process Description for Glycol Dehydration Units................ 6-5 6.2.2 Benzene Emissions from Glycol Dehydration Units............... 6-8 6.2.3 Controls and Regulatory Analysis........................... 6-13 6.3 PETROLEUM REFINERY PROCESSES.......................... 6-14 6.3.1 Description of Petroleum Refineries ......................... 6-14 6.3.2 Benzene Emissions from Petroleum Refinery Processes and Operations ............................................ 6-17 6.3.3 Controls and Regulatory Analysis........................... 6-28 6.4 GASOLINE MARKETING..................................... 6-31 6.4.1 Benzene Emissions from Loading Marine Vessels............... 6-34 6.4.2 Benzene Emissions from Bulk Gasoline Plants and Bulk Gasoline Terminals............................................. 6-37 6.4.3 Benzene Emissions from Service Stations..................... 6-46 6.4.4 Control Technology for Marine Vessel Loading ................ 6-49 6.4.5 Control Technology for Gasoline Transfer .................... 6-53 6.4.6 Control Technology for Gasoline Storage..................... 6-53 6.4.7 Control Technology for Vehicle Refueling Emissions ............ 6-56 6.4.8 Regulatory Analysis ..................................... 6-58 6.5 PUBLICLY OWNED TREATMENT WORKS...................... 6-59 6.5.1 Process Description of POTWs............................. 6-59 6.5.2 Benzene Emissions From POTWs........................... 6-68 6.5.3 Control Technologies for POTWs........................... 6-69 6.5.4 Regulatory Analysis ..................................... 6-72 6.6 MUNICIPAL SOLID WASTE LANDFILLS........................ 6-72 6.6.1 Process Description of MSW Landfills ....................... 6-73 6.6.2 Benzene Emissions from MSW Landfills ...................... 6-74 6.6.3 Control Technologies for MSW Landfills ..................... 6-80 6.6.4 Regulatory Analysis ..................................... 6-81 6.7 PULP, PAPER, AND PAPERBOARD INDUSTRY .................. 6-81 6.7.1 Process Description for Pulp, Paper, and Paperboard Making Processes ............................................. 6-82 6.7.2 Benzene Emissions from Pulp, Paper and Papermaking Processes . 6-91 vi TABLE OF CONTENTS, continued Section Page 6.8 SYNTHETIC GRAPHITE MANUFACTURING..................... 6-93 6.8.1 Process Description for Synthetic Graphite Production........... 6-94 6.8.2 Benzene Emissions from Synthetic Graphite Production.......... 6-97 6.8.3 Control Technologies for Synthetic Graphite Production.......... 6-99 6.9 CARBON BLACK MANUFACTURE............................. 6-99 6.9.1 Process Description for Carbon Black Manufacture............. 6-101 6.9.2 Benzene Emissions from Carbon Black