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Addressing the concerns related to fluoropolymers
during their lifecycle
OECD Global forum on PFAS
Deepak Kapoor
Gujarat Fluorochemicals
February 13, 2024
1
Fluoropolymers are a critical component of
modern society
• to ensure safety & well-being;
• unlock innovation & technological advancements;
• implement decarbonization technologies and achieve environmental sustainability
2
(non-polymeric) PFAS emissions’ management
during fluoropolymer lifecycle
• Manufacturing phase
o Recycling/reuse of unreacted PFAS intermediates
o Responsible use/Phasing out of PFAS polymerization aids
o Abatement of by-products
• Use phase
o Fluoropolymers are highly stable and do not degrade to non-polymeric PFAS
o Limited wide dispersive consumer uses – powders & mixtures
• End of life phase
o Complete mineralization when incinerated – no generation of non-polymeric PFAS
o Fluoropolymer waste is chemically inert - does not partition to air, water & soil
3
Unreacted monomer recovery/reuse (PTFE)
4
The unreacted monomer, TFE, is collected through
a vent recovery process and sent to the monomer
recycling unit where - after purification - the
monomer is stored in storage tanks for reuse in
the polymerization process.
This is a continuous closed loop system that
ensures that the monomer does not get released
to the environment.
Being insoluble in water, TFE is not present in the
polymer latex and also not released into the
coagulation drain water. Therefore, the chance of
monomer emissions is considered negligible.
TFE is not a PFAS as per OECD definition.
Abatement / Phase-out of PFAS polymerization aids
• PFAS polymerization aids do not get consumed during polymerization
• Raw materials, by-products and degradation products may also be PFAS
• PFAS polymerization aids are partially recovered/reused & abated:
o Recycling: 80-85 %
o Capture: ~99 %
o Destruction: ~100 %
Fluoropolymer manufacturers are developing and shifting to non-PFAS polymerization aids
5
Abatement of PFAS by-products
• Unintentional generation vary depending upon product, process and polymerization aids used
• Concentrations are limited (PTFE produced with hydrocarbon polymerization aid)
• Targeted PFAS measured using UPLC-MS/MS –
o less than 5 ppb (sum of 70 PFAS)
o EU REACH proposal limit – 250 ppb (sum)
• Non-targeted PFAS measured using LC-HRMS –
o single digit ppm (without abatement)
o << 1ppm (with abatement)
o 1ppm PFAS x 50,000 tons of fluoropolymers = 50 Kgs per annum
6
Abatement technologies
7
Shifting paradigms in PFAS resin removal with biomaterial alternatives
H. Karimi-Maleh et al.
The Use phase
• Fluoropolymers are mainly used in industrial set-ups as articles and components
• The use of fluoropolymers as powders and mixtures in wide dispersive consumer applications
e.g. cosmetics, ski-waxes, inks, TULAC applications is insignificant (<1%).
• The high molecular weight of fluoropolymers makes it difficult to penetrate human proteins
and therefore bio-accumulation is highly unlikely.
• Fluoropolymers are not bioavailable. Bioavailability is necessary for bioaccumulation. To
establish this, GFL is working on a project with US EPA to generate toxico-kinetics data on key
fluoropolymers.
8
Fluoropolymers satisfy OECD’s Polymers of low concern
criteria
9
The End-of-Life phase
Incineration
84%
Landfill
13%
Recycling
3%
10
Conversio GmbH study 2022 in EEA
Fluoropolymer incineration project
Research partner Karlsruhe Institute of Technology (KIT), Germany
Sampling partner SGS Institut Fresenius GmbH, Industries & Environment, Germany
Laboratory partner SGS Belgium NV, Institute for Applied Chromatography, Belgium
Feed sampling Pro-K, Fluoropolymer processing and DU association, Germany
Incineration Advisor Dr. Philip Taylor, P Taylor & Associates, LLC, USA
Academic Consultant Dr. Bruno Ameduri, University of Montpellier, France
Data quality review Environmental Standards Inc., USA
Observer Umweltbundesamt (German Federal Environment Agency)
A pilot scale trial at conditions similar to household and industrial waste-to-energy 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
11
KIT test facility - BRENDA
The BRENDA plant is a large facility that is a good representation of commercial waste-to-energy plants
12
Process conditions:
• 860OC for 2 sec
• 1100OC for 2 sec
Fluoropolymer
feed:
• PTFE
• PVDF
• PFA
• FKM
Modified OTM-45
sampling method
Incineration results
Fluorine recovery: Ranged from 69 to 84% using Tunable Diode Laser - provides strong evidence
for the complete mineralization of fluoropolymer feed mixture
Trifluoroacetic acid: Not detected for all samples at a reporting limit of 14 µg/m3
PFAS analysis: A large majority of samples (> 98% of samples) indicated that targeted short &
long-chain PFAS were non-detectable at levels of < 1 ng/m3
PFAS analyses of wastewater and ash residue: Non-detectable with reporting limits of 0.02 µg/l
GC-MS analysis for ultra short chain fluorocarbons: Non-detectable at a reporting limit of 5-30
µg/m3
*Peer-reviewed full report will be published in Chemosphere - Q2 2024
13
Landfilling
• Fluoropolymer waste is chemically inert, extremely stable and do not partition to
air/water/soil*
• Studies conducted on PTFE to investigate potential degradation support stability of PTFE and
lack of transformation to other PFAS**
• Fluoropolymers disposed in landfills do not pose any threat to environment
e.g. PTFE is used as an inert geomembrane solution in the US***
14
* Danish EPA report, **Charles River Laboratory and ALS studies, *** Tippet et. al., 2023
Key messages
• Fluoropolymers are safe & critical for the functioning of modern society
• Release of non-polymeric PFAS during fluoropolymer lifecycle is effectively managed by:
• Implementing recovery & reuse of unreacted raw materials
• Responsible use / Phasing out use of PFAS polymerisation aids
• Implementing abatement technologies to arrest unintentional by-products
• Labelling/regulating wide dispersive consumer applications to ensure proper disposal at EOL
• Fluoropolymers can be manufactured & processed responsibly
• Fluoropolymers can be safely and sustainably managed at end-of-life
15
Suggested future work for OECD
• Globally uniform definition of hazard associated to PFAS (PBT, vPvB, PMT, vPvM) – persistency
alone does not amount to hazard
• Greater emphasis on principle of proportionality in regulatory processes with focus on
emissions control & limiting exposure
• Considerations needed to check impacts due to regulatory controls in other countries
16
Thank you!
17

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OECD Global Forum on the Environment dedicated to Per- and Polyfluoroalkyl Substances: Addressing the concerns related to fluoropolymers during their lifecycle [ Deepak Kapoor

  • 1. Addressing the concerns related to fluoropolymers during their lifecycle OECD Global forum on PFAS Deepak Kapoor Gujarat Fluorochemicals February 13, 2024 1
  • 2. Fluoropolymers are a critical component of modern society • to ensure safety & well-being; • unlock innovation & technological advancements; • implement decarbonization technologies and achieve environmental sustainability 2
  • 3. (non-polymeric) PFAS emissions’ management during fluoropolymer lifecycle • Manufacturing phase o Recycling/reuse of unreacted PFAS intermediates o Responsible use/Phasing out of PFAS polymerization aids o Abatement of by-products • Use phase o Fluoropolymers are highly stable and do not degrade to non-polymeric PFAS o Limited wide dispersive consumer uses – powders & mixtures • End of life phase o Complete mineralization when incinerated – no generation of non-polymeric PFAS o Fluoropolymer waste is chemically inert - does not partition to air, water & soil 3
  • 4. Unreacted monomer recovery/reuse (PTFE) 4 The unreacted monomer, TFE, is collected through a vent recovery process and sent to the monomer recycling unit where - after purification - the monomer is stored in storage tanks for reuse in the polymerization process. This is a continuous closed loop system that ensures that the monomer does not get released to the environment. Being insoluble in water, TFE is not present in the polymer latex and also not released into the coagulation drain water. Therefore, the chance of monomer emissions is considered negligible. TFE is not a PFAS as per OECD definition.
  • 5. Abatement / Phase-out of PFAS polymerization aids • PFAS polymerization aids do not get consumed during polymerization • Raw materials, by-products and degradation products may also be PFAS • PFAS polymerization aids are partially recovered/reused & abated: o Recycling: 80-85 % o Capture: ~99 % o Destruction: ~100 % Fluoropolymer manufacturers are developing and shifting to non-PFAS polymerization aids 5
  • 6. Abatement of PFAS by-products • Unintentional generation vary depending upon product, process and polymerization aids used • Concentrations are limited (PTFE produced with hydrocarbon polymerization aid) • Targeted PFAS measured using UPLC-MS/MS – o less than 5 ppb (sum of 70 PFAS) o EU REACH proposal limit – 250 ppb (sum) • Non-targeted PFAS measured using LC-HRMS – o single digit ppm (without abatement) o << 1ppm (with abatement) o 1ppm PFAS x 50,000 tons of fluoropolymers = 50 Kgs per annum 6
  • 7. Abatement technologies 7 Shifting paradigms in PFAS resin removal with biomaterial alternatives H. Karimi-Maleh et al.
  • 8. The Use phase • Fluoropolymers are mainly used in industrial set-ups as articles and components • The use of fluoropolymers as powders and mixtures in wide dispersive consumer applications e.g. cosmetics, ski-waxes, inks, TULAC applications is insignificant (<1%). • The high molecular weight of fluoropolymers makes it difficult to penetrate human proteins and therefore bio-accumulation is highly unlikely. • Fluoropolymers are not bioavailable. Bioavailability is necessary for bioaccumulation. To establish this, GFL is working on a project with US EPA to generate toxico-kinetics data on key fluoropolymers. 8
  • 9. Fluoropolymers satisfy OECD’s Polymers of low concern criteria 9
  • 11. Fluoropolymer incineration project Research partner Karlsruhe Institute of Technology (KIT), Germany Sampling partner SGS Institut Fresenius GmbH, Industries & Environment, Germany Laboratory partner SGS Belgium NV, Institute for Applied Chromatography, Belgium Feed sampling Pro-K, Fluoropolymer processing and DU association, Germany Incineration Advisor Dr. Philip Taylor, P Taylor & Associates, LLC, USA Academic Consultant Dr. Bruno Ameduri, University of Montpellier, France Data quality review Environmental Standards Inc., USA Observer Umweltbundesamt (German Federal Environment Agency) A pilot scale trial at conditions similar to household and industrial waste-to-energy 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 11
  • 12. KIT test facility - BRENDA The BRENDA plant is a large facility that is a good representation of commercial waste-to-energy plants 12 Process conditions: • 860OC for 2 sec • 1100OC for 2 sec Fluoropolymer feed: • PTFE • PVDF • PFA • FKM Modified OTM-45 sampling method
  • 13. Incineration results Fluorine recovery: Ranged from 69 to 84% using Tunable Diode Laser - provides strong evidence for the complete mineralization of fluoropolymer feed mixture Trifluoroacetic acid: Not detected for all samples at a reporting limit of 14 µg/m3 PFAS analysis: A large majority of samples (> 98% of samples) indicated that targeted short & long-chain PFAS were non-detectable at levels of < 1 ng/m3 PFAS analyses of wastewater and ash residue: Non-detectable with reporting limits of 0.02 µg/l GC-MS analysis for ultra short chain fluorocarbons: Non-detectable at a reporting limit of 5-30 µg/m3 *Peer-reviewed full report will be published in Chemosphere - Q2 2024 13
  • 14. Landfilling • Fluoropolymer waste is chemically inert, extremely stable and do not partition to air/water/soil* • Studies conducted on PTFE to investigate potential degradation support stability of PTFE and lack of transformation to other PFAS** • Fluoropolymers disposed in landfills do not pose any threat to environment e.g. PTFE is used as an inert geomembrane solution in the US*** 14 * Danish EPA report, **Charles River Laboratory and ALS studies, *** Tippet et. al., 2023
  • 15. Key messages • Fluoropolymers are safe & critical for the functioning of modern society • Release of non-polymeric PFAS during fluoropolymer lifecycle is effectively managed by: • Implementing recovery & reuse of unreacted raw materials • Responsible use / Phasing out use of PFAS polymerisation aids • Implementing abatement technologies to arrest unintentional by-products • Labelling/regulating wide dispersive consumer applications to ensure proper disposal at EOL • Fluoropolymers can be manufactured & processed responsibly • Fluoropolymers can be safely and sustainably managed at end-of-life 15
  • 16. Suggested future work for OECD • Globally uniform definition of hazard associated to PFAS (PBT, vPvB, PMT, vPvM) – persistency alone does not amount to hazard • Greater emphasis on principle of proportionality in regulatory processes with focus on emissions control & limiting exposure • Considerations needed to check impacts due to regulatory controls in other countries 16