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Home My WebLink AboutDEQ-CFW_00086055is • Vinyl Ethers North Air Emissions Inventory 2008 AIR EMISSIONS INVENTORY SUPPORTING DOCUMENTATION Emission Source ID No: NS-B Emission Source Description: VE-North PPVE Manufacturing Process PPVE Process Emissions Page 1 of 14 Process & Emission Description: The VE-North PPVE manufacturing process is a continuous chemical reaction. All emissions from the process are vented through the Nafion Division Waste Gas Scrubber (Control Device ID No. NCD-Hdr) which has a documented control efficiency of 99.6% for all acid fluoride compounds. Some emitted compounds are assumed to pass completely through the scrubber, so the control efficiency for those compounds is assumed to be 0%. The control of emissions of specific compounds will be addressed and detailed in the following pages. The PPVE process in VE-North emits compounds in the acid fluoride family. In the presence of water (such as in atmospheric moisture), these acid fluorides can eventually hydrolyze to hydrogen fluoride. For the purpose of this emissions inventory, a conservative approach will be taken and the acid fluorides will be reported both as a VOC and as the equivalent quantity of hydrogen fluoride. Basis and Assumptions: - The PPVE process flowsheet is the basis for relative concentrations of before -control emissions of gaseous wastes. - Calculations of point source emissions are based on actual vent flow totals taken from the IP21 Historian. - All emission determination calculations are available on the EXCEL spreadsheet found at S:/Everyone/martinas/Emissions/2008/VEN Air Emissions 2008.xls. DEQ-CFW 00086055 Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Page 2 of 14 IsPoint Source Emission Determination A. Hexafluoropropylene (HFP) HF Potential: HFP is a VOC without the potential to form HF Quantity Released HFP is a byproduct present in the HFPO feed. It is an inert in VE-North that is vented to the WGS. FIFP vented per the process flowsheet 0.05 kg HFP Vented from the Condensation Reactor: 2.35 kg CondRxVentFlO 0.01 kg HFP Vented from the Crude Receiver 3.97 kg Crude Receiver Vent 0.01 kg HFP Vented from the Foreshots Receiver 1.06 kg ForeshotsReceiver Vent 30 kg HFP 100 kg Stripper Vent Vented from the Stripper HFP vented based on 4,143 kg total Condensation Reactor vent stream (22266FG). HFP vented based on 5,814 kg total Crude Receiver vent stream (22701FG). HFP vented based on 1,636 kg total Foreshots Receiver vent stream (22826FG). HFP vented based on 12,085 kg in the Stripper vent stream (22231FC). HFP vented from Condensation Reactor: 0.05 kg FIFP x 4,143 kg CndRX = 96 kg HFP 2.35 kg CndRx HFP vented from Crude Receiver 0.01 kg HFP x 5,814 kg CrRec = 20 kg HFP 3.97 kg CrRec HFP vented from Foreshots Receiver 0.01 kg HFP x 1,636 kg FsRec = 14 kg HFP 1.06 kg FsRec HFP vented from Stripper 30 kg HFP x 12,085 kg Strpr = 3,626 kg HFP 100 kg Strpr VOC Emissions 96 kg from Condensation Reactor + 20 kg from Crude Receiver + 14 kg from Foreshots Receiver 3,626 kg from Stripper CAS No.116-15-4 DEQ-CFW 00086056 Vinyl Ethers North • E • Air Emissions Inventory 3,756 kg HFP 3,756 kg VOC 8,280 lb VOC PPVE Process Emissions Page 3 of 14 DEQ-CFW 00086057 Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Page 4 of 14 B. Hexafluoropropylene oxide (BFPO) CAS No. 428-59-1 HF Potential: BFPO is a VOC without the potential to form HF Quantity Released BFPO unreacted in condensation is vented to the WGS. BFPO vented per the process flowsheet 0.11 kg HFPO Vented from the Condensation Reactor: 2.35 kg Cond Rx Vent Flow Vented from the Crude Receiver 0 kg HFPO 3.97 kg Crude Receiver Vent 0 kg HFPO Vented from the Foreshots Receiver 1.06 kg ForeshotsReceiverVen Vented from the Stripper 60 kg HFPO 100 kg Stripper Vent BFPO vented based on 4,143 kg total Condensation Reactor vent stream (22266FG). BFPO vented based on 5,814 kg total Crude Receiver vent stream (22701FG). BFPO vented based on 1,636 kg total Foreshots Receiver vent stream (22826FG). BFP vented based on 12,085 kg in the Stripper vent stream (22231FC). BFPO vented from Condensation Reactor: 0.11 kg BFPO x 4,143 kg CndRx — 200 kg BFPO 2.35 kg CndRx HFPO vented from Crude Receiver 0.00 kg BFPO x 5,814 kg CrRec = 0 kg HFPO 3.97 kg CrRec HFPO vented from Foreshots Receiver 0.00 kg HFPO x 1,636 kg FsRec — 0 kg HFPO 1.06 kg FsRec HFP vented from Stripper 60 kg BFPO x 12,085 kg Strpr — 7,251 kg HFPO 100 kg Strpr VOC Emissions 200 kg from Condensation Reactor + 0 kg from Crude Receiver + 0 kg from Foreshots Receiver + 7,251 kg from Stripper = 7,452 kg HFPO = 7,452 kg VOC 16,428 Ib VOC • DEQ-CFW 00086058 Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Page 5 of 14 C. Perfluoropropionyl fluoride (PPF) HF Potential: Ee mole of PPF (MW = 166) can generate 1 mole of HF (MW = 20). 1 molePPF 20g HF 1 moleHF kgPPF- = 0.120kgH1 166g PPF 1 moleHF 1 molePPF Therefore, each 1 kg of PPF generates 0.120 kg of HF Quantity Released Before -control PPF vented per the process flowsheet Vented from the Condensation Reactor: 2.14 kg PPF 2.35 kg Cond Rx Vent Flow Vented from the Crude Receiver 0 kg PPF 3.97 kg Crude Receiver- Vent 0 kg PPF Vented from the Foreshots Receiver 1.06 kg ForeshotsReceiverT/en Vented from the Stripper 10 kg PPF 100 kg Stripper Vent PPF vented based on 4,143 kg total Condensation Reactor vent stream (22266FG). PPF vented based on 5,814 kg total Crude Receiver vent stream (22701FG). PPF vented based on 1,636 kg total Foreshots Receiver vent stream (22826FG). PPF vented based on 12,085 kg in the Stripper vent stream (22231FC). Before control PPF vented from Condensation Reactor: 2.14 kg PPF x 4,143 kg CndRx = 3,766 kg PPF 2.35 kg CndRx PPF vented from Crude Receiver 0.00 kg PPF x 5,814 kg CrRec = 0 kg PPF 3.97 kg CrRec PPF vented from Foreshots Receiver 0.00 kg PPF x 1,636 kg FsRec = 0 kg PPF 1.06 kg FsRec PPF vented from Stripper 10 kg PPF x 12,085 kg Strpr = 1,209 kg PPF 100 kg Strpr Total before -control PPF vented = 4,975 kg PPF After -control emissions utilizing the 99.6% control efficient Waste Gas Scrubber (WGS): CAS No. 422-61-7 VOC Emissions 4,975 kg PAF Waste Gas Scrubber x (100%-99.6%) 20 kg PAF = 20 kg VOC 44 Ib. VOG HF Equivalent Emissions_ 20 kg PAF x 0.120 kg HF/kg PAF 2 kg HF = 5.3 Ib. HF DEQ-CFW 00086059 Vinyl Ethers North Air Emissions Inventory D. Tetrafluoroethylene (TFE) HF Potential: TFE is a VOC without the potential to form HF Quantity Released TFE is a byproduct that can be formed in the ABR system. It is an inert in VE-North that is vented to the WGS. TFE vented per the process flowsheet 0 kg TFE Vented from the Condensation Reactor: 2.35 kg Cond Rx Vent Flow 2.17 kg TFE Vented from the Crude Receiver 3.97 kg Crude Receiver Vent 0.0045 kg TFE Vented from the Foreshots Receiver 1.06 kg Foreshot.5ReceiverVent 0 kg TFE Vented from the Stripper 100 kg Stripper Vent TFE vented based on 4,143 kg total Condensation Reactor vent stream (22266FG). TFE vented based on 5,814 kg total Crude Receiver vent stream (22701FG). TFE vented based on 1,636 kg total Foreshots Receiver vent stream (22826FG). TFE vented based on 12,085 kg in the Stripper vent stream (22231FC). TFE vented from Condensation Reactor: 0.00 kg TFE x 4,143 kg CndRx = 0 kg TFE 2.35 kg CndRx TFE vented from Crude Receiver 2.17 kg TFE x 5,814 kg CrRec = 3,176 kg TFE 3.97 kg CrRec TFE vented from Foreshots Receiver 0.0045 kg TFE x 1,636 kg FsRec = 7 kg WE 1.06 kg FsRec TFE vented from Stripper 0 kg TFE x 12,085 kg Strpr = 0 kg TFE 100 kg Strpr VOC Emissions 0 kg from Condensation Reactor + 3,176 kg from Crude Receiver + 7 kg from Foreshots Receiver + 0 kg from Stripper = 3,183 kg TFE = 3,183 kg VOC 7,018 lb VOC PPVE Process Emissions Page 6 of 14 CAS No. 116-14-3 DEQ-CFW 00086060 Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Page 7 of 14 , E. Perfluoropropyl vinyl ether (PPVE) CAS No. 1623-5-8 HF Potential: PPVE is a VOC without the potential to form HF Quantity Released PPVE vented per the process flowsheet 0kgPPVE Vented from the Condensation Reactor: 2,35 kg Cond Rx Vent Flow 0.50kgPPVE Vented from the Crude Receiver 3.97 kg Crude Receiver Vent 0.88 kg PPVE 1.06 kg ForeshotsReceiverVent Vented from the Foreshots Receiver 0 kg PPVE Vented from the Stripper 100 kg Stripper Vent PPVE vented based on 4,143 kg total Condensation Reactor vent stream (22266FG). PPVE vented based on 5,814 kg total Crude Receiver vent stream (22701FG). PPVE vented based on 1,636 kg total Foreshots Receiver vent stream (22826FG). PPVE vented based on 12,085 kg in the Stripper vent stream (22231FC). PPVE vented from Condensation Reactor: 0.00 kg PPVE x 4,143 kg CndRx — — 0 kg PPVE 2.35 kg CndRx PPVE vented from Crude Receiver 0.50 kg PPVE x 5,814 kg CrRec = 739 kg PPVE 3.97 kg CrRec PPVE vented from Foreshots Receiver 0.88 kg PPVE x 1,636 kg FsRec = 1,357 kg PPVE 1.06 kg FsRec PPVE vented from Stripper 0 kg PPVE x 12,085 kg Stier = 0 kg PPVE 100 kg Strpr VOC Emissions 0 kg from Condensation Reactor + 739 kg from Crude Receiver + 1,357 kg from Foreshots Receiver + 0 kg from Stripper 2,096 kg PPVE = 2,096 kg VOC 4,620 lb VOC • DEQ-CFW 00086061 Vinyl Ethers North Air Emissions Inventory isF. Perlluoro-2-butene (C4) HF Potential: C4s are VOCs without the potential to form HF Quantity Released C4s are perfluorobutenes that are byproducts from the Agitated Bed Reactor system. They are inerts in VE-North that are vented to the WGS. C4s vented per the process flowsheet 0 kg C4s Vented from the Condensation Reactor: 2.35 kg Cond Rx Vent Flow 0.01 kg C4s Vented from the Crude Receiver 3.97 kg Crude Receiver Vent 0.15 kg C4s Vented from the Foreshots Receiver 1.06 kg ForeshotsReceiveYVent 0 kg C4s Vented from the Stripper 100 kg Stripper Vent C4s vented based on 4,143 kg total Condensation Reactor vent stream (22266FG). C4s vented based on 5,814 kg total Crude Receiver vent stream (22701FG). C4s vented based on 1,636 kg total Foreshots Receiver vent stream (22826FG). C4s vented based on 12,085 kg in the Stripper vent stream (22231FC). C4s vented from Condensation Reactor: 0.00 kg C4s x 4,143 kg CndRx = 0 kg C4s 2.35 kg CndRx C4s vented from Crude Receiver 0.01 kg C4s x 5,814 kg CrRec = 13 kg C4s 3.97 kg CrRec C4s vented from Foreshots Receiver 0.15 kg C4s x 1,636 kg FsRec = 231 kg C4s 1.06 kg FsRec C4s vented from Stripper 0 kg C4s x 12,085 kg Strpr = 0 kg C4s 100 kg Strpr VOC Emissions 0 kg from Condensation Reactor + 13 kg from Crude Receiver + 231 kg from Foreshots Receiver + 0 kg from Stripper 244 kg C4s = 244 kg VOC 538 1b VOC • PPVE Process Emissions Page 8 of 14 CAS No. 360-89-4 DEQ-CFW 00086062 • 9 0 Vinyl Ethers North Air Emissions Inventory G. Pertluoropentene (C5) HF Potential: C5s are VOCs without the potential to form HF Quantity Released C5s are perfluoropentenes that are byproducts from the Agitated Bed Reactor system. They are inerts in VE-North that are vented to the WGS. C5s vented per the process flowsheet 0 kg C5s Vented from the Condensation Reactor: 2.35 kg Cond Rx Vent Flow 0 kg C5s Vented from the Crude Receiver 3.97 kg Crude Receiver Vent 0.02 kg C5s Vented from the Foreshots Receiver 1.06 kg ForeshotsReceiverVent Vented from the Stripper 0 kg C5s 100 kg Stripper Vent C5s vented based on 4,143 kg total Condensation Reactor vent stream (22266FG). C5s vented based on 5,814 kg total Crude Receiver vent stream (22701FG). C5s vented based on 1,636 kg total Foreshots Receiver vent stream (22826FG). C5s vented based on 12,085 kg in the Stripper vent stream (22231FC). C5s vented from Condensation Reactor: 0.00 kg C5s x 4,143 kg CndRx = 0 kg C5s 2.35 kg CndRx C5s vented from Crude Receiver 0.00 kg C5s x 5,814 kg CrRec = 0 kg C5s 3.97 kg CrRec C5s vented from Foreshots Receiver 0.02 kg C5s x 1,636 kg FsRec = 28 kg C5s 1.06 kg FsRec Cos vented from Stripper 0 kg C5s x 12,095 kg Strpr = 0 kg C5s 100 kg Strpr VOC Emissions 0 kg from Condensation Reactor + 0 kg from Crude Receiver + 28 kg from Foreshots Receiver + 0 kg from Stripper = 28 kg C5s = 28 kg VOC 62 lb VOC PPVE Process Emissions Page 9 of 14 CAS No. 376-87-4 DEQ-CFW 00086063 Vinyl Ethers North Air Emissions Inventory H. Carbon Monoxide (CO) HF Potential: CO can not form HF (quantity Released CO is a byproduct from the Agitated Bed Reactor system. This inert in VE-North that are vented to the WGS. CO vented per the process flowsheet 0kgCO Vented from the Condensation Reactor: 2.35 kg Cond Rx Vent Flow 1.27 kg CO Vented from the Crude Receiver 3.97 kg Crude Receiver Vent 0kgCO Vented from the Foreshots Receiver 1.06 kg ForeshotsReceiverVent 0 kg CO Vented from the Stripper 100 kg Stripper Vent CO vented based on 4,143 kg total Condensation Reactor vent stream (22266FG). CO vented based on 5,814 kg total Crude Receiver vent stream (22701FG). CO vented based on 1,636 kg total Foreshots Receiver vent stream (22826FG). CO vented based on 12,085 kg in the Stripper vent stream (22231FC). CO vented from Condensation Reactor: _ 0.00 kg CO x 4,143 kg CndRx = 0 kg CO 2.35 kg CndRx CO vented from Crude Receiver 1.27 kg CO x 5,814 kg CrRec = 1,865 kg CO 3.97 kg CrRec CO vented from Foreshots Receiver _ 0.00 kg CO x 1.06 kg FsRec CO vented from Stripper _ 0 kg CO x 100 kg Strpr CO Emissions 1,636 kg FsRec = 12,085 kg Strpr = 0 kg from Condensation Reactor 1,865 kg from Crude Receiver 0 kg from Foreshots Receiver 0 kg from Stripper 1,865 kg CO = 0 kg CO 0 kg CO PPVE Process Emissions Page 10 of 14 CAS No. 630-08-0 4,111 lb CO (not a VOC) DEQ-CFW 00086064 Vinyl Ethers North Air Emissions Inventory 1. Acetonitrile (AN) HF Potential AN is a VOC and Hazardous Air Polluntant without the potential to form HF. Quantity Released AN emissions based on 8,066 kg AN fed Hydrocarbon waste sent to Hydrocarbon waste tank = 4,936 kgs H/C waste PPVE generated during the year 134,322 kg PPVE Assume that: 5% of spent acetonitrile are fluorocarbons. AN portion of hydrocarbon waste stream: 4,936 kg to H/C waste x (1-(.1)) 4,689 kg AN to H/C waste Material Balance Based on total Vinyl ether produced 134,322 kg PPVE Assume 90% Crude is needed to generage that amount of PPVE 70% of AF going to ABR is needed to create the Crude Feed going to ABR is 1,500 ppm AN 1,000,000 Therefore: VOC Emission AN only used during a PPVE Campaign Total AN 134,322 kg PPVE \ 0.90 Crude \ 0.70 AF x 0.0015 ppm AN 320 kg AN in Feed to ABR 8,066 kg AN fed 4,689 kg AN to H/C waste 320 kg AN to ABR 3,057 kg AN 3,057 kg VOC 6,739 lb VOC 6,739 lb VOC PPVE Process Emissions Page 11 of 14 CAS No. 75-05-8 DEQ-CFW 00086065 Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Page 12 of 14 J. VOC Summary Nafion Compound Name Before Control Generated After Control Stack Emissions kg/yr Ib/ r VOC Ib/yr A. HFP 3,756 8,280 8,280 B. HFPO 7,452 16,428 16,428 C. PPF 4,975 10,967 44 D. TFE 3,183 7,018 7,018 E. PPVE 2,096 4,620 4,620 F. C4 244 538 538 G. C5 28 62 62 I. AN 3,057 6,739 6,739 Total 24,790 54,652 43,729 • U DEQ-CFW 00086066 • • 11 Vinyl Ethers North Air Emissions Inventory K. Total Emission Summary** ** All Emissions in this table represent "After Control" emissions. PPVE Process Emissions Page 13 of 14 Nafion Compound Name Process Emissions lb/yr Equipment Emissions (Notch lb/ r Maintenance Emissions (Not.2) lb/yr Total Emissions lb/yr A. HFP 8,280 4 0 8,284 B. HFPO 16,428 292 17 16,738 C. PPF 44 0 1 45 D. TFE 7,018 0 0 7,018 E. IPPVE 4,620 480 487 5,587 F. C4 538 46 66 650 G. C5 62 0 0 62 H. CO (not a VOC) 0 0 4,111 I. AN 120 7 6,739 * HFPO-Diener 6 36 42 * BFPO Trimer 0 1 1 Total 36,990 949 1 615 49,276 Note 1 - See section titled "Equipment Emissions" for details Note 2 - See section titled "Maintenance Emissions" for details CO not realistically expected through equipment or maintenance emissions AN total based on material balance, see section K. * Not normally emitted from the process as a routine stack emission DEQ-CFW 00086067 • • Vinyl Ethers North L. HF Equivalent Emissions Air Emissions Inventory PPVE Process Emissions Page 14 of 14 Nafion Compound Name Process Emissions lb/ r Equipment Emissions lb/yr Maintenance Emissions lb! r Total Emissions lb/yr C. PPF 5.3 0.0 0.15 5.44 * BFPO-Dimer 0.4 2.15 2.52 * HYPO Trimer 0.0 0.03 0.03 Total 5.3 0 2.33 7.99 * Not normally emitted from the process as a routine stack emission The estimated BF equivalent emissions were determined by multiplying the total emission quantity of an acid fluoride by the ratio of the molecular weight of HF divided by the molecular weight of the specific acid fluoride. This is based on the fact that one mole of an acid fluoride will generate one mole of BF. For example, if 1001b. of PPF was emitted: 20 lb/mol HF 166 lb/mol PPF X 100 lb/yr Equipment PPF = 12.0 lb/yr HF DEQ-CFW 00086068