August 2014 Emissions Estimation Protocol for Petroleum Refineries Draft Version 3 Submitted to: Office of Air Quality Planning and Standards U.S. Environmental Protection Agency Research Triangle Park, NC 27711 Submitted by: RTI International 3040 Cornwallis Road Research Triangle Park, NC 27709-2194 [This page intentionally left blank.] Emissions Estimation Protocol for Petroleum Refineries Draft Version 3 Table of Contents Table of Contents 1. Introduction ......................................................................................................................................... 1-1 1.1 Completeness ............................................................................................................................ 1-1 1.2 Data Quality ............................................................................................................................ 1-10 1.3 Calculations and Significant Digits ........................................................................................ 1-10 2. Equipment Leaks ................................................................................................................................. 2-1 2.1 Methodology Rank 1 for Equipment Leaks.............................................................................. 2-2 2.2 Methodology Rank 2 for Equipment Leaks.............................................................................. 2-3 2.2.1 Speciating Equipment Leak Emissions ....................................................................... 2-5 2.2.2 Calculating Hourly and Annual Equipment Leak Emissions ..................................... 2-7 2.3 Methodology Rank 3 for Equipment Leaks............................................................................ 2-10 2.3.1 Speciating Equipment Leak Emissions ..................................................................... 2-12 2.3.2 Calculating Hourly and Annual Equipment Leak Emissions ................................... 2-12 2.4 Methodology Ranks 4 and 5 for Equipment Leaks ................................................................ 2-13 2.4.1 Speciating Equipment Leak Emissions ..................................................................... 2-14 2.4.2 Calculating Hourly and Annual Equipment Leak Emissions ................................... 2-17 3. Storage Tanks ...................................................................................................................................... 3-1 3.1 Methodology Rank 1 for Storage Tanks ................................................................................... 3-1 3.2 Methodology Rank 2 for Storage Tanks ................................................................................... 3-2 3.3 Methodology Rank 3 for Storage Tanks ................................................................................... 3-4 4. Stationary Combustion Sources .......................................................................................................... 4-1 4.1 Methodology Rank 1 for Stationary Combustion Sources ....................................................... 4-2 4.2 Methodology Rank 2 for Stationary Combustion Sources ....................................................... 4-5 4.3 Methodology Rank 3A for Stationary Combustion Sources .................................................... 4-9 4.4 Methodology Rank 3B for Stationary Combustion Sources .................................................. 4-10 4.5 Methodology Rank 4 for Stationary Combustion Sources ..................................................... 4-11 4.5.1 Default Emission Factors for Process Heaters .......................................................... 4-12 4.5.2 Default Emission Factor for Internal Combustion Engines ...................................... 4-18 4.5.3 Default Emission Factors for Combustion Turbines ................................................. 4-18 5. Process Vents ...................................................................................................................................... 5-1 5.1 Catalytic Cracking Units .......................................................................................................... 5-1 5.1.1 Methodology Ranks 1 and 2 for Catalytic Cracking Units ......................................... 5-2 5.1.2 Methodology Ranks 3 and 4 for Catalytic Cracking Units ......................................... 5-2 5.1.3 Methodology Rank 5A for CCU Metal HAP Emissions Estimates ............................ 5-7 5.1.4 Methodology Rank 5B for Catalytic Cracking Units ................................................ 5-10 5.2 Fluid Coking Units ................................................................................................................. 5-11 5.2.1 Methodology Ranks 1 and 2 for Fluid Coking Units ................................................ 5-12 5.2.2 Methodology Ranks 3 and 4 for Fluid Coking Units ................................................ 5-12 5.2.3 Methodology Rank 5 for Fluid Coking Units ........................................................... 5-12 5.3 Delayed Coking Units ............................................................................................................ 5-12 5.3.1 Methodology Ranks 1 and 2 for Delayed Coking Units ........................................... 5-14 5.3.2 Methodology Rank 3 for Delayed Coking Units ...................................................... 5-14 5.3.3 Methodology Rank 4 for Delayed Coking Units ...................................................... 5-16 5.3.4 Methodology Rank 5 for Delayed Coking Units ...................................................... 5-17 5.4 Catalytic Reforming Units ...................................................................................................... 5-17 5.4.1 Emissions Estimation Methodology for Catalytic Reforming Units ........................ 5-18 5.5 Sulfur Recovery Plants ........................................................................................................... 5-19 iii Emissions Estimation Protocol for Petroleum Refineries Draft Version 3 Table of Contents 5.5.1 Methodology Ranks 1 and 2 for Sulfur Recovery Plants .......................................... 5-20 5.5.2 Methodology Ranks 3 and 4 for Sulfur Recovery Plants .......................................... 5-20 5.5.3 Methodology Rank 5 for Sulfur Recovery Plants ..................................................... 5-21 5.6 Other Miscellaneous Process Vents ....................................................................................... 5-21 5.6.1 Hydrogen Plant Vents ............................................................................................... 5-22 5.6.2 Asphalt Plant Vents ................................................................................................... 5-22 5.6.3 Coke Calcining.......................................................................................................... 5-24 5.6.4 Blowdown Systems ................................................................................................... 5-27 5.6.5 Vacuum Producing Systems ..................................................................................... 5-27 6. Flares ................................................................................................................................................... 6-1 6.1 Methodology Rank 1 for Flares ................................................................................................ 6-2 6.2 Methodology Rank 2 for Flares ................................................................................................ 6-3 6.3 Methodology Rank 3 for Flares ................................................................................................ 6-4 6.4 Methodology Rank 4 for Flares ................................................................................................ 6-6 6.5 Methodology Ranks 5 and 6 for Flares .................................................................................... 6-7 7. Wastewater Collection and Treatment Systems .................................................................................. 7-1 7.1 Methodology Rank 1 for Wastewater Treatment Units ............................................................ 7-2 7.2 Methodology Rank 2 for Wastewater Treatment Units ............................................................ 7-2 7.2.1 Wastewater Collection Systems .................................................................................. 7-3 7.2.2 Primary Weirs ............................................................................................................. 7-5 7.2.3 Oil-Water Separators .................................................................................................. 7-5 7.2.4 Dissolved Air Flotation Units ..................................................................................... 7-6 7.2.5 Equalization Tanks ...................................................................................................... 7-6 7.2.6 Biological Treatment Units ......................................................................................... 7-6 7.2.7 Polishing Ponds ........................................................................................................... 7-8 7.2.8 Site-Specific Factors ................................................................................................... 7-8 7.2.9 Model Validation .......................................................................................................