UNITED STATES ENVIRONMENTAL PROTECTION AGENCY REGION 5 77 WEST JACKSON BOULEVARD CHICAGO, ILLINOIS 60604 SUBJECT: CLEAN AIR ACT INSPECTION REPORT Union Carbide Corporation, Hahnville, Louisiana FROM: Victoria Nelson, Environmental Engineer AECAB (MI/WI) THRU: Sarah Marshall, Section Supervisor AECAB (MI/WI) TO: File Basic Information Facility Name: Union Carbide Corporation (UCC) Facility Location: 355 LA Highway 3 142, Hahnville, Louisiana Dates of Inspection: April 19 - 20, 2022 EPA Inspectors: 1. Victoria Nelson, EPA Region 5, Environmental Engineer 2. Karina Kuc, EPA Region 5, Environmental Engineer 3. Sarah Frey, EPA Region 6, Physical Scientist 4. James Haynes, EPA Region 6, Physical Scientist 5. Christopher Williams, EPA OECA, Chemical Engineer 6. Rich Helmich, EPA NEIC, Chemist 7. Ali Gitipour, EPA ORD, Federal Postdoctoral Research Fellow - Chemical Engineer 8. David Mahoney, EPA NEIC, Technical Coordinator Other Attendees: 1. Charles Cuti, UCC, Leveraged Air Specialist 2. Brendan Chambon, UCC, Environmental Air Specialist 3. Brandon Saunier, Louisiana Department of Environmental Quality, Environmental Scientist 4. Irving Range, Think Environmental, Operations Manager 5. Dennis Fleming, Think Environmental, Site Supervisor 6. Jeff Lyons, Think Environmental, LDAR Technician ------- Contact Email Address: Charles Cuti - CRCuti@dow.com Purpose of Inspection: To evaluate compliance with the Clean Air Act Facility Type: Organic Chemical Manufacturing Regulations Central to Inspection: National Emission Standards for Benzene Waste Operations, 40 C.F.R. Part 61, Subpart FF; National Emission Standards for Organic Hazardous Air Pollutants (NESHAP) from the Synthetic Organic Chemical Manufacturing Industry, 40 C.F.R. Part 63, Subparts F, G, and H (HON); NESHAP for Ethylene Manufacturing Process Units, 40 C.F.R. Part 63, Subpart XX; NESHAP for Miscellaneous Organic Chemical Manufacturing, 40 C.F.R. Part 63, Subpart FFFF (MON) April 19, 2022 Arrival Time: 9:15 AM CT Departure Time: 5:30 PM CT April 20, 2022 Arrival Time: 8:45 AM CT Departure Time: 5:40 PM CT Inspection Type: M Unannounced Inspection ~ Announced Inspection Opening Conference M Presented Credentials M Stated authority and purpose of inspection M Small Business Resource Information Sheet not provided. Reason: Not a small business M Provided CBI warning to facility The following information was obtained verbally from Charles Cuti and Brendan Chambon unless otherwise noted. Company Ownership: UCC is a subsidiary of the Dow Chemical Company. In December 2020, Vopak Industrial Infrastructure Americas St. Charles, LLC (Vopak) became the owner of the storage tanks that support raw material, product, and wastewater storage and associated transfer operations for the UCC facility. The storage tanks and associated equipment are co- located with the UCC facility. Process Description: UCC operates several chemical manufacturing process units at the Hahnville facility. A majority of the storage tanks used to store raw material, product, and wastewater are owned and operated Page 2 of 6 ------- by Vopak. There are six ethylene oxide (EO) storage tanks (Tanks 2400 - 2405) that remain under the ownership and operation of UCC. The six EO tanks are referred to as the "EO Mound" and are underground. The EO Mound tanks are vented to a scrubber for EO recovery and then to a steam-assisted flare for control, denoted as Flare 507 in the corresponding Title V Permit. Tank loading operations are controlled by a vapor balance system. The "Olefins Plant" contains two olefins process units that produce 1,3-butadiene, ethylene, acetylene and propylene from ethane and propane cracking. Naptha is stored at Vopak and is a raw material for the process, along with ethane and propane that UCC receives by pipeline. The raw materials are introduced to a furnace that is fueled with natural gas and methane. There are 11 furnaces in which cracking occurs. Following cracking, the process stream goes through a quench system and then through an acid gas system. Next, the process stream goes through a series of distillation columns to separate out 1,3-butadiene, ethylene, acetylene, and propylene. Most of the ethylene produced goes to other process units on-site. A portion is sent off-site to other Dow facilities. The olefins units produce benzene-containing wastewater that is subject to treatment under Subpart FF. Wastewater streams are transferred through the unit via open drain systems and then stored in Tanks 1301,1311,1321, and 1331 at the Vopak terminal. Wastewater is transferred back to UCC and is treated in three oil-water separators and three wastewater strippers in the olefins units for benzene removal. UCC uses a continuous analyzer to detect the concentration of organic material in the wastewater following treatment in the process unit. The wastewater stream will be retreated at the oil-water separators and wastewater strippers until it meets the minimum concentration to be transferred to the on-site wastewater treatment operation. Non-benzene containing wastewater from the other process units is routed to the on-site wastewater treatment operation. The wastewater treatment plant includes a large, open aeration pond. UCC does not monitor these wastewater streams for concentrations of organic hazardous air pollutants (HAP). Periodically, UCC collects samples from the wastewater sumps (the point prior to transfer to the wastewater treatment plant) at each process unit and has them analyzed for concentrations of organic compounds. The "Oxides Plant" produces EO with ethylene and oxygen in the presence of a silver catalyst. Following the formation of EO, an analyzer is used to measure the product stream. The sample line for the analyzer, denoted as 46R and EQT 120 in the corresponding UCC Title V Permit, vents to atmosphere. A steam-assisted flare controls emissions from the Oxides Plant. The EO is used on-site in other process units and also sent off site by rail. The "Polyethers Plant" is a batch process unit that operates with EO as a raw material. The "Amines Plant" contains three process units that produce ethylene amines, ethanol amines, and other various amines. EO and ammonia are raw materials for some of the units. The "Acrylics Plant" consists of multiple process units that produces acrylic acid, acrolein, heavy esters, 2-ethylhexyl aery I ate, and methyl acrylate. A steam-assisted flare controls emissions from the Acrylics Plant. Page 3 of 6 ------- Staff Interview: UCC has approximately 900 employees and operates the Hahnville facility 24 hours a day for seven days a week. The scrubber used for EO recovery at the storage tanks header prior to flaring was brought online in March 2021. A design evaluation was done for the scrubber and no testing has been performed. Recently, one of the Acrylics Plant process units was converted from ethyl aery I ate production to produce methyl acrylate. Interview of Dennis Fleming, Site Supervisor and Irving Range, Operations Manager with Think Environmental: Think Environmental staff perform LDAR monitoring for the UCC facility, as well as for the co-located terminal operated by Vopak. Think Environmental LDAR Technicians use ThermoFisher Toxic Vapor Analyzer 1000 flame ionization detectors (TVA 1000) to conduct EPA Method 21 monitoring. Prior to use, each TVA 1000 is calibrated using methane span gases of 500,1,000, 5,000, and 10,000 parts per million (ppm). EPA reviewed calibration records that showed past usage of isobutylene calibration gases. In April 2021, Think Environmental technicians switched from using Phoenix 21 photo ionization detectors to the TVA 1000 FID. Tour Information EPA Tour of the Facility: Yes Data Collected and Observations: EPA inspectors observed organic emissions at storage tanks operated by Vopak using the FLIR GFx-320 and a flame ionization detector (FID). Think Environmental LDAR Technician, Jeff Lyons, confirmed EPA's FID readings with the FID regularly used for LDAR monitoring conducted on-site. Photos and/or Videos: were taken during the inspection. EPA inspectors recorded videos using the FLIR GFx-320. See Appendix A. Field Measurements: were taken during this inspection. EPA inspectors collected organic emissions data using a FID. See Appendix B. EPA also toured the facility with a mobile air monitoring unit, or geospatial measurement of air pollution (GMAP), and collected air canister samples for lab analysis. The results from the GMAP and air samples will be detailed in a separate report. With the GMAP, EPA detected elevated EO concentrations that appeared to be from an open sample line associated with an analyzer in the Oxides Plant. EPA also observed with the GMAP elevated benzene concentrations at the base of Tanks 1301,1311,1321, and 1331. Additional GMAP results were noted during the inspection and will be included in the comprehensive report. Page 4 of 6 ------- Records Review 1. Sample LDAR Calibration Records from 2018 - 2022 2. Notifications of Compliance Status for process units subject to the HON and MON Closing Conference M Provided U.S. EPA point of contact to the facility Requested documents: • Current permits for each process unit • LDAR Database for the previous five years • Notifications of Compliance Status for the HON, MON, Subpart FF, and Subpart XX • Semi-annual and quarterly compliance reports for MON, HON, and Subpart FF, 2020 - • Wastewater sumps sampling results, 2018 - 2022 • Monthly benzene stripper samples, Jan. 2022 - March 2022 • Process flow diagrams for each process unit and wastewater streams • Wastewater emission calculations • Site-wide annual emissions calculations for 2020 and 2021 • Benzene wastewater analyzer data, 2020 - 2022 • Total Annual Benzene reports, 2020 and 2021 • Completed work orders for leaks identified during the inspection • Flare 507 - "EO Flare" Emission Calculations Compliance Assistance: EPA recommended repair of the leaks identified during the inspection, see Appendix B. Concerns: EPA noted that open drain hubs throughout the olefins units, which UCC staff believed were part of the process unit's wastewater transfer system, were observed with detectable emissions. Digital Signatures 2021 VICTORIA Report Author: NELSON Digitally signed by VICTORIA NELSON Date: 2022.05.16 11:42:03 -05'00' SARAH Section Supervisor: MARSHALL Digitally signed by SARAH MARSHALL Date: 2022.05.16 12:10:28 -05'00' Page 5 of 6 ------- Facility Name: Union Carbide Corporation Facility Location: 355 LA Highway 3142, Hahnville, Louisiana Date of Inspection: April 19-20, 2022 Appendices and Attachments 1. Appendix A: Digital Video and Image Log 2. Appendix B: EPA Monitoring Results and Calibration Information Page 6 of 6 ------- ------- Facility Name: Union Carbide Corporation Facility Location: 355 LA Highway 3142, Hahnville, Louisiana Date of Inspection: April 19-20, 2022 Appendix A: Digital Video and Image Log 1. Inspector Name: Karina Kuc, Victoria Nelson Archival Record Location: Region 5 Electronic Records Center Image Number File Name Date and Time (Central time)* Description of Image 1 MOV_0218.mp4 4/19/2022 15:35 Olefins 1 Flare 2 MOV_0219.mp4 4/19/2022 15:39 Sewer grate in Olefins 1 3 MOV_0220.mp4 4/19/2022 15:41 Sewer grate in Olefins 1 4 MOV_0221.mp4 4/19/2022 15:52 Boiler feed water pump 5 MOV_0222.mp4 4/19/2022 15:54 Stack for Furnace 11 6 MOV_0223.mp4 4/19/2022 16:35 Lummus furnace stack 7 MOV_0224.mp4 4/20/2022 15:47 Leak on equipment LDAR ID: 36963 8 MOV_0225.mp4 4/20/2022 15:49 Leak on methane column reformer pump - tag frozen therefore ID couldn't be read 9 MOV_0226.mp4 4/20/2022 15:59 Leak on equipment LDAR ID: R4655.1 10 IR_0228J pg 4/20/2022 16:17 Leak on equipment LDAR ID: R4655.1 11 MOV_0229.mp4 4/20/2022 16:30 Leak on control valve at the base of FA-3208 12 MOV_0230.mp4 4/20/2022 16:37 Leak on equipment LDAR ID: 1036 13 MOV_0231.mp4 4/20/2022 17:16 Leak on methane line 14 MOV_0232.mp4 4/20/2022 17:18 Leak on flare sweep line (methane) no LDAR ID 15 IR_0233J pg 4/20/2022 17:33 Wastewater drain hub open to atmosphere 16 IR_0234J pg 4/20/2022 17:35 Wastewater drain hub open to atmosphere 17 IR_0235J pg 4/20/2022 17:35 Wastewater drain hub open to atmosphere, plugged with a pad 18 MOV_0236.mp4 4/20/2022 17:46 Process line overflowing into stormwater sewer 19 MOV_0239.mp4 4/21/2022 12:25 Union Carbide Oxides Flare and Thermal Oxidizer stack 20 MOV_0240.mp4 4/21/2022 12:26 Union Carbide Acrylics Flare - EPA observed smoke from the Acrylics flare at the flame. 21 MOV_0244.mp4 4/21/2022 13:08 Union Carbide Oxides Flare and Thermal Oxidizer stack "The time reflected on the timestamp is an hour later than the video was recorded. Appendices Page 1 of 5 ------- Facility Name: Union Carbide Corporation Facility Location: 355 LA Highway 3142, Hahnville, Louisiana Date of Inspection: April 19-20, 2022 Appendix B: EPA Monitoring Results and Calibration Instrumentation Monitoring Results from Inspection 4/19/2022 - 4/20/2022 and Calibration and Instrument Information Table 1. Monitoring of Process Equipment and Wastewater Transfer Points Equipment Location Notes EPA Inspector Date EPA Reading (ppm) Think Environmental Reading (ppm) Open drain North Quench Victoria N. 4/19/2022 650 248 hub Area of the Olefins 1 Unit Valve R50667 Olefins 2 Unit C2 Column Victoria N. 4/20/2022 894 1028 Stormwater Beneath Victoria N. 4/20/2022 25 81 drain Deethanizer Reflux Pump in Olefins 2 Unit Valve R41618 Methane Column Reflux Drum (FA-3311) Victoria N. 4/20/2022 1,700 1,020 Connector Methane Column Victoria N. 4/20/2022 1,229 2,505 R36963 in Olefins 2 Unit Pump Methane Column Reformer Tag number was frozen over and could not be observed. Significant emissions were observed from equipment at the Methane Column in the Olefins 2 Unit. Victoria N. 4/20/2022 1,200 2,876 Connector At the base of the Leak at the drain Victoria N. 4/20/2022 > 80,000 9,092 R4655.1 Methane Column #3 Feed Separator line to the flare Connector At the base of Methane Feed Stripper (DA- 3302) in Olefins 2 Unit No LDAR tag. Potential leak from the insulation in this area. Victoria N. 4/20/2022 >20,000 9,999 Pressure Next to No LDAR tag. Victoria N. 4/20/2022 4,000 — Regulator Instrument 4234 at Gypsy Line Knock-Out Pot Appendices Page 2 of 5 ------- Facility Name: Union Carbide Corporation Facility Location: 355 LA Highway 3142, Hahnville, Louisiana Date of Inspection: April 19-20, 2022 Valve At Methane Line from C2 Dryer in Olefins 2 Unit Not part of the LDAR program. Victoria N. 4/20/2022 8,000 10,000 Control Valve Leak from Process Line at Base of FA-3208 Not part of the LDAR program. Visible leak - equipment covered in yellow material. Could not find the highest leak point due to significant, overwhelming odors. Victoria N. 4/20/2022 >1,000 OEL At base of line to the Propylene Accumulator. Below Valve 1036. Victoria N. 4/20/2022 >10,000 9,000 Control Valve Fuel gas line from another process unit feeding to the fuel drum No LDAR tag. Victoria N. 4/20/2022 >10,000, Flame out 7,888 Valve Flare Sweep line next to Ethane Feed Preheater No LDAR tag and not in the LDAR program. Victoria N. 4/20/2022 802 Valve Flare Sweep line next to Ethane Feed Preheater No LDAR tag and not in the LDAR program. Victoria N. 4/20/2022 >10,000 9,821 Connector Flare Sweep line next to Ethane Feed Preheater No LDAR tag and not in the LDAR program. Victoria N. 4/20/2022 >10,000 Open drain hub Next to Valve 9708 J. Lyons observed the reading on EPA's instrument Victoria N. 4/20/2022 810 210 Open drain hub Next to Flux Oil Tank Containment area Victoria N. 4/20/2022 880 Charles Cuti confirmed the reading on EPA's instrument. J. Lyons left the tour at the end Appendices Page 3 of 5 ------- Facility Name: Union Carbide Corporation Facility Location: 355 LA Highway 3142, Hahnville, Louisiana Date of Inspection: April 19-20, 2022 of his shift at 4:30 PM. Open drain Near Flux Oil Victoria N. 4/20/2022 275 C. Cuti hub Tank Containment area confirmed the reading on EPA's instrument. Open drain Near Flux Oil Victoria N. 4/20/2022 112 C. Cuti hub Tank Containment area confirmed the reading on EPA's instrument. Open drain Near Flux Oil Victoria N. 4/20/2022 111 C. Cuti hub Tank Containment area confirmed the reading on EPA's instrument. Open drain Near Flux Oil Victoria N. 4/20/2022 350 C. Cuti hub Tank Containment area confirmed the reading on EPA's instrument. Open drain Near Flux Oil Victoria N. 4/20/2022 120 C. Cuti hub Tank Containment area confirmed the reading on EPA's instrument. Background At base of A process sewer Victoria N. 4/20/2022 15 reading furnace hub was overflowing to a nearby stormwater drain that drains to an open oil skimmer prior to wastewater treatment on- site. Legend: Used to denote that J. Lyon's confirmation reading was not given to EPA or that J. Lyons was not available to confirm the reading. OEL - Open-ended valve or line Appendices Page 4 of 5 ------- Facility Name: Union Carbide Corporation Facility Location: 355 LA Highway 3142, Hahnville, Louisiana Date of Inspection: April 19-20, 2022 Calibration and Instrument Information EPA used one ThermoFisher Toxic Vapor Analyzers 2020 (TVA2020). The EPA TVA2020 response times are in the 4 to 5 second range. During the inspection, Jeff Lyons, Think Environmental LDAR Technician, used a flame ionization detector (FID), model ThermoFisher Toxic Vapor Analyzer 1000, to confirm EPA's readings. All readings were collected on April 19-20, 2022. Victoria Nelson used TVA2020 ID: SL1555 for the duration of the survey. Table 2. Instrument Calibration April 19, 2022 SL1555 Reading (ppm) 1:45pm Calibration Reading, 500 ppm 496 1:45pm Calibration Reading, 10,000 ppm 10,300 April 20, 2022 SL1555 Reading (ppm) 2:17pm Calibration Reading, 500 ppm 499 2:17pm Calibration Reading, 10,000 ppm 10,300 5:10pm Drift Check, 500 ppm 520 5:10pm Drift Check, 10,000 ppm 10,600 Table 3. Calibration Gases Manufacturer Composition Lot# Expiration TG Technical Services Zero air TDBJ-1-22 3/27/2023 TG Technical Services Methane, 500 ppm TDBJ-150A-500-11 3/27/2023 TG Technical Services Methane, 1% TIBJ-135A-1-1 8/21/2023 Appendices Page 5 of 5 ------- |