Document bOE2wy3zw8O9ejJXxbL2zzZDO

Incineration of Fluoropolymers Project presentation Ref. Ares(2024)2544971 - 08/04/2024 , Karlsruhe Institute of Technology (KIT) , SGS Belgium NV P Taylor & Associates, LLC 15th June 2023 1 Incineration of fluoropolymers: PFAS analysis along the flue gas pathway A pilot scale trial at conditions similar to household and industrial wastetoenergy incineration plants that typically burn products containing fluoropolymers was conducted to assess the potential generation of any statistically significant uncontrolled emissions of Per and Polyfluorinated Alkyl Substances (PFAS) at levels that might present a risk 2 Research partner Sampling partner Laboratory partner Feed sampling Incineration Advisor Academic Consultant Data quality review (under process) Observer Project partners Institute for Technical Chemistry (ITC) at Karlsruhe Institute of Technology (KIT) SGS Institut Fresenius GmbH, Industries & Environment SGS Belgium NV, Institute for Applied Chromatography ProK, Fluoropolymer processing and downstream user association, Germany LLC, USA ICGM, University of Montpellier, France Environmental Standards Inc., USA UBA, Umweltbundesamt (German Federal Environment Agency) 3 Experimental Setup test parameters start-up with natural gas and oil number of HF and PFAS sampling starting solid feeding (wood chips) locations duration [hrs] 24 RUN 24 date / remarks 25.2.23; 10 a.m. 26.2.23; 10 a.m. day 1 and 2 day background of rotary kiln / combustion chamber with 3 oil, natural gas and 100 kg/h wood chips 11 1 27.2.2023; 9 am day 3 Monday solid fuel: woodchip (100 no Top of post- 9 kg/h) + 320 g/h FP together TPCC: 860 C; combustion with oil and natural gas 2.0 s chamber (E1b), 3 after boiler, stack 11 background of rotary kiln / no 13 combustion chamber with oil, natural gas and 100 kg/h wood chips 3 11 Change of temperature post combustion chamber 12 feeding of fluoropolymers over night 2 28.2.2023; 9 am stop feeding flouropolymers in the evening day 4 Tuesday 3 01.03.2023; 9 am day 5 Wednesday over night background of rotary kiln / combustion chamber with 3 oil, natural gas and wood chips 11 4 02.03.2023; 9 am day 6 Thursday solid fuel: woodchip (100 no kg/h) + 320 g/h FP together TPCC: 1100 C; with oil and natural gas 2.0 s 3 background of rotary kiln / no combustion chamber with oil, natural gas and 100 kg/h wood chips 3 Top of post- 9 combustion chamber (E1b), after boiler, stack 11 13 11 feeding of fluoropolymers over night 5 03.03.2023; 9 am stop feeding flouropolymers in the evening day 7 Friday 6 04.03.2023; 9 am day 8 Saturday shut down 24 day 9 6 Material Mass fraction [wt.-%] PTFE tubes 63,00 PTFE tape 7,00 PVDF 18,00 PFA 6,00 FKM rubber 6,00 mass flow = 320 g/h Basis of fluoropolymer feed mixture: 1. Feed mixture comprises of 4 largest volume fluoropolymers PTFE, PVDF, PFA, FKM. Together these represent 80% of commercial fluoropolymer production 2. ProK supplied fluoropolymer samples of major applications that were grinded and mixed Main Operational Parameters, Setting 1 and 2 Rotary kiln mass flow wood chips main air mass flow heating oil volume flow natural gas volume flow combustion air inclination rotation speed temperature flue gas outlet thermal power unit kg/h mN3/h kg/h mN3/h mN3/h rev p.m. C MW setting S1 RUN 1, 2, 3 98 setting S2 RUN 4, 5, 6 98 418 423 61 46 4 4 872 753 2 0.2 0.4 800 - 900 1.1 0.9 Increase of rotation speed to avoid slagging - 200 kW, shift thermal power to the PCC combustion chamber volume flow natural gas to burner D4.1 sum of volume flow combustion air to burner D4.1 volume flow natural gas to burner D4.2 sum of volume flow combustion air to burner D4.2 residence time temperature flue gas post-combustion chamber outlet (with control) CO (level E2) O2 (level E2) thermal power total thermal power rotary kiln and post combustion chamber mN3/h mN3/h mN3/h mN3/h s C mg/m3 Vol.-% dry MW MW 22 35 671 429 22 35 671 428 2 860 1095 0.2 1.2 11.2 7.0 0.46 0.72 1.59 1.67 Increase of temperature by reduction of stochiometric ratio + 260 kW constant boiler / fluegas volume flow O2 CO water vapour 7 mN3/h Vol.-% dry mg/m3 Vol.-% wet 3958 11.9 1.35 6.20 3238 9.0 1.64 8.49 PFAS analysis 1. Modified OTM45 for sampling train 2. Combustion Ion Chromatography (CIC) for Adsorbable Organic Fluorine (AOF) 3. UltrahighPerformance Liquid Chromatography coupled to tandem Mass Spectrometer (UPLCMS/MS) for targeted long chain PFAS 4. Gas chromatography coupled to mass spectrometry (GCMS) for volatile Fluorocarbons 5. Ion chromatography (IC) for Trifluoroacetic Acid (TFA) 6. Ion Selective Electrode (ISE) for Inorganic Fluoride 7. Tunable Diode laser for Hydrogen fluoride 8 Modified OTM45 sampling train 9 Testing methodology 24 samples analyzed per setting 3 samples were collected and analyzed at each sampling point per setting (triplicate sampling) PFAS analyzed at Prerun, Run and Postrun conditions Ash samples were analyzed for target PFAS content Blank media and solutions were analyzed for their respective parameters Blank sample train were analyzed after every run at relevant sample locations 10 HF measurement after the boiler (Tunable Diode Laser) 11 Fluorine balance (based on HFLaser) 12 Summary of analytical results (860C) Post combustion After Boiler Avg. Total Fluorine (mg/m3) (LOQ (gas) - 27 g/m3) (LOQ (part) - 1.7 g/m3) 36.5 17.3 Avg. AOF (LOQ 27 g/m3) 31.5 Nondetectable Stack Nondetectable Nondetectable Sum of PFAS (ng/m3) 1.5 0.3 5.1 TFA (LOQ - 14 g/m3) Nondetectable Nondetectable Nondetectable 13 Results from GCMS analysis (50 samples) Short chain fluorocarbons Tetrafluoromethane Hexafluoroethane Trifluoromethane Hexafluoropropylene Pentafluoroethane Octafluorocyclobutane LOQ (g/m) 20 30 20 5 25 25 Results (Stack) Non detectable except 2 values in separate runs near detection limits (20, 27 g/m) Non detectable Non detectable Non detectable Non detectable Non detectable 14 Total expected PFAS emissions from EU incineration plants Total waste incinerated in the EU = 62 million tons per year* Maximum sum of PFAS released (stack) at 860C/1100C with 0.3 % FP feed = 18.4 ng/m3 N, dry assuming PFAS < LOQ = 0 Specific Flue gas amount released per ton of waste** Total load of PFAS emitted in the EU But, Actual fluoropolymer waste incinerated (85% of 52,000 tons) = 4060 m3 N, dry = 4.63 kilograms per year for 0.3% FP feed = 44,200 tons per year (0.07% of total waste) Therefore, total PFAS emissions in the EU should be lower than 4.63 kilograms per year *https://ec.europa.eu/eurostat/statisticsexplained/index.php?title=Municipal_waste_statistics#Municipal_waste_generation **VDI guideline 3925 "Methods for evaluation of waste treatment processes" 15 Results Fluorine Recovery: Fluorine recoveries ranged from 69 to 84% using Tunable Diode Laser provides strong evidence for mineralization of the Fluoropolymer feed mixture Trifluoroacetic acid: TFA was not detected for all samples at a reporting limit of 14 g/m3 Targeted PFAS analysis: A large majority of samples (> 99% of samples associated with 860C condition and > 98% of samples associated with 1100C condition) indicated that longchain PFAS were nondetectable at levels of < 1 ng/m3 PFAS analysis of wastewater and ash residue: A large majority of the samples were nondetectable with reporting limits of 0.02 g/l GCMS analysis for short chain fluorocarbons: Nondetectable at a reporting limit of 530 g/m3 levels 16 Conclusions Fluoropolymers are converted to inorganic fluorides (hydrogen fluoride) and carbon dioxide The absence of organic fluorides and PFAS confirms complete mineralization of fluoropolymers Therefore, fluoropolymers do not generate any measurable levels of small molecule PFAS of concern Standard wastetoenergy incineration operating conditions are sufficient for mineralization of fluoropolymers Fluoropolymers pose no risk to human health and the environment at their end of life when incinerated 17 Thank you 18