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Chemical recycling of fluoropolymers
Closing the fluo19r9i7n-2e022loop
Thorsten Gerdes, Achim Schmidt Rodenkirchen, Klaus Hintzer
SKZ - Innovations using Fluoropolymers 03.05. - 04.05.2023, Wrzburg/Rottendorf
Chemical recycling of fluoropolymers
Institut fr Innovative VerfahrensGteerdcehs 0n5i/k202e3.V.
Institute in cooperation with the University of Bayreuth Interdisciplinary applied research and development in the field of combined electrothermal
processes and process intensification since 1997.
Non-profit organization
Chemical recycling of fluoropolymers
Gerdes 05/2023
Decoupling of value creation & human wellbeing from resource consumption
Circular Economy as contribution to the EU target of net zero greenhouse gas emissions, allowing economic growth to be decoupled from resource consumption.
Dissipation
Minimise
Dissipation
https://www.eea.europa.eu/soer/2020/soer-2020-visuals/circular-economy-system-diagram/view Chemical recycling of fluoropolymers
Dissipation Dissipation
Gerdes 05/2023
Circular economy for fluoropolymers
Mechanical recycling
Chemical recycling
C. Linder, H. Beylage und J. Hein, ,,Fluorpolymer waste in Europe 2020 - End-of-Life (EOL) analysis of fluoropolymer applications, products and associated waste streams," Conversio / proK Fachgruppe, 2022
Chemical recycling of fluoropolymers
Gerdes 05/2023
Polymers waste EoL options based on the EU Waste Framework Directive
https://www.mdpi.com/2073-4360/13/5/713 Chemical recycling of fluoropolymers
Gerdes 05/2023
EoL fluorinated polymer material flows in Europe in 2020
?
Burning/damping
13,1% Landfill
Desired process
MSWI/ RDF/ SR
72%
EoL-waste collected 23,5 kt (100%)
Energy recovery
Sec. Metal production
11.5%
3.4%
0% (?) ?
Reuse
Reduce waste
Recycling
Data from: C. Linder, H. Beylage und J. Hein, ,,Fluorpolymer waste in Europe 2020 - End-of-Life (EOL) analysis of fluoropolymer applications, products and associated waste streams," Conversio / proK Fachgruppe, 2022
Chemical recycling of fluoropolymers
Gerdes 05/2023
The world of fluorine
Villalba, Ayres und Schroder, ,,Accounting for fluorine: production use and loss," Journal of Industrial Ecology, 2008 Chemical recycling of fluoropolymers
Gerdes 05/2023
Synthesis of fluoropolymers
Chemical recycling of fluoropolymers
Gerdes 05/2023
Fluoropolymer production: consumption of resources
Based on the production of 1 t PTFE
Chemical recycling of fluoropolymers
Gerdes 05/2023
Energy demand for PTFE-production
24,6%
37,3%
23,9%
10,5%
3,2%
0,5%
220 MJ/kg
Abraham, V., Comparative life cycle assessment and environmental impacts of PTFE production and recycling, Master thesis, University Bayreuth, Germany 2013 Chemical recycling of fluoropolymers
Gerdes 05/2023
Cumulative Energy Demand (CED) of bulk plastics
POLYSTYRENE (PS) POLYETHYLENE (PE) POLYETHYLENETEREPHTHALATE (PET) POLYTETRAFLUOROETHYLENE (PTFE)
71 65 54
220 MJ/kg polymer
Shen, L., Nieuwlaar, E., Worrell, E., and Patel, M. K., Life cycle energy and GHG emissions of PET recycling: Change-oriented effects, International Journal of Life Cycle Assessment 16 (2011) Patel, M., KEA (Cumulative Energy Demand) fr Produkte der Organischen Chemie, Working paper of project no. 104 01 123 for the German Environment Agency (Bundesumweltamt)
Chemical recycling of fluoropolymers
Gerdes 05/2023
Global polymer production 2021
Fluoropolymers 0,5
Bio-based plastics 5,9
PS
20,7
PUR
21,5
PET
24,2
Other thermoplastics
26,6
Other thermosets
28,1
Recycled plastics
32,4
PVC
50,4
PP
PE
0,0
20,0
40,0
60,0
Total: 390.7 Mt
75,4 80,0
105,1 100,0
120,0
https://plasticseurope.org/knowledge-hub/plastics-the-facts-2022/ https://en.kunststoffe.de/a/specialistarticle/fluoroplastics-245074
Chemical recycling of fluoropolymers
million tons
Gerdes 05/2023
R&D in the field of FP-recycling
Monomer recycling
Molecule recycling
,,Fluorspar recycling"
Feedstock recycling
TRL of processes developed by InVerTec between 4 (plasma) and 8 (Depolymerization)
Chemical recycling of fluoropolymers
Gerdes 05/2023
Feedstock recycling: Combustion of partially fluorinated polymers
Ethylen - Tetrafluorethylen Copolymer (ETFE)
Mass [%]
coke Combustion of coke
Temperature [C]
Chemical recycling of fluoropolymers
RH = -2100 kJ/mol
Feedstock recycling
Feeder
Fluidized bed reactor Sorption cascade
Gerdes 05/2023
Conversion of calcite into syn-spar
Chemisorption & conversion: CaCO3 + 2 HF CaF2 + CO2 + H2O
Feedstock recycling
Shrinking unreacted-core Modell: Core-Shell-structure Steady movement of the
reaction front into the core
40 m
Chemical recycling of fluoropolymers
40 m
40 m
Gerdes 05/2023
Design of a 900t p.a. plant for syn-spar production from HF
Vacuum belt filters Exhaust gas treatment Syn-spar removal
Stirring tank
Chemical recycling of fluoropolymers
Feedstock recycling
Calcite feeder
Neutralization Reactor
Gerdes 05/2023
Monomer Recycling: Plasma-pyrolysis of perfluorinated alkanes
Plasma converting alkanes (<C4) into alkenes
Monomer recycling
Process and apparatus for producing fluorinated alkenes
Post-pyrolysis
Conversion rate Yield
Chemical recycling of fluoropolymers
WO2016/054246 A1
Gerdes 05/2023
Molecule recycling: Dissolving of ionomer membranes
Molecule recycling
solvent
water membrane
Hydrothermal Batch 230C 40 bar
Pro: Scalable no CO2 emissions Most efficient technology Cons: not established TRL~4 Purification steps not defined
purification
recasting PTFE support
membrane
Impurities
depolymerisation
PTFE
Yield: 90% Energy demand: app. 166 MJ/kg
Chemical recycling of fluoropolymers
Gerdes 05/2023
Monomer Recycling: Depolymerisation of PTFE
Monomer recycling
Fluidized bed reactor
Chemical recycling of fluoropolymers
Control room
Gerdes 05/2023
Thermal decomposition (pyrolysis) of PTFE
PTFE
TFE (Tetrafluoroethylene)
Carbon
Fluorine
C-F ~490 kJmol-1
C-C ~340 kJmol-1
Fluorine as the most electron-negative element builds very strong bonds with carbon
Heat
Chemical recycling of fluoropolymers
Gerdes 05/2023
Depolymerisation of PTFE
Chemical recycling of fluoropolymers
Monomer recycling
Gerdes 05/2023
Depolymerisation of PTFE particles in a fluidized bed
Monomer recycling
C3F6 Ar
CF
C2F4 C F
24
CF
C F 2 4 C2F4
36
36
+ C2F4
C 4F8 :CF :CF2 :CF
C2F4
2
2
C2F4
C 4F8 C2F4 :CF2
:CF2 C F
Ar
:CF2
:CF2 2 4
Ar
C3F6
C F C2F4 :CF2
:CF2 C F
PTFE 3 6
C2F4
C3F6 :CF2
24
:CF2 C3F6
C3F6
C2F4
C2F4 C2F4
:CF2
:CF2
C2F4
C F :CF2 :CF :CF2 C2F4 C F
C3F6
24
CF
2
24
Ar
36
CF
C2F4
Ar
C 2F 4
48
C4F8 C F
C 2F 4
24
Temperature rises to >500 C :CF2 is formed on the particle; particle shrinks 2 :CF2 = C2F4 (TFE); C2F4 removal; reproduction
CF2 + C2F4 = C3F6 (HFP) C3F6 removal; reproduction
CF2 + C3F6 = 2 C4F8 C4F8 removal; reproduction no reaction of 2 C4F8 due to too low concentration
Chemical recycling of fluoropolymers
Gerdes 05/2023
Influence of the fluoropolymer on the product gas
Monomer recycling
Yield
Chemical recycling of fluoropolymers
Gerdes 05/2023
Environmental benefit from depolymerisation of PTFE
Monomer recycling
Chemical recycling of fluoropolymers
Related to the production of 1000 t PTFE
Gerdes 05/2023
PTFE pyrolysis plant at 3M / Dyneon
500 t/a Fluoropolymers valuable products: TFE, HFP, cyclo C4F8 Simple but efficient process design Robust against impurities High monomer yield The chemical recycling of fluoropolymers on a technical scale was demonstrated successfully.
Monomer recycling
Chemical recycling of fluoropolymers
Burgkirchen, Germany, 2015
Gerdes 05/2023
Summery
Chemical recycling is mandatory to ensure the sustainable future of fluoropolymers Depending on the kind and composition of EoL fluoropolymers, the type of chemical recycling has to
be adapted: Molecular Recycling Monomer recycling Feedstock recycling
For all variants of chemical recycling, a TRL of at least 4 has been demonstrated Due to the quite differentiated uses of fluoropolymers, proper recycling is complex Production waste recycling is the "low hanging fruit" It is not the lack of suitable concepts but the "valley of death" in process scaling that is currently
hindering development
Chemical recycling of fluoropolymers
Gerdes 05/2023
Closing the fluorine loop partners & sponsors
Chemical recycling of fluoropolymers
Gerdes 05/2023
9
Activities along the process chain element
Development of business models for EoL-material based fluorochemicals Development of waste management strategies for end-of-life materials Quality management for secondary raw materials
(quality control and pre-treatment of EoL-material) Design and engineering of Up-Cycling plants
In cooperation with Producers of fluorochemicals/-polymers Processors of fluoropolymers / end users Recycling companies Associations & policy makers
closing the loop
www.element9.de
Gerdes 05/23
The mission / Bussines Units
9
element
Engineering & Up-Cycling plants
Establishing processes for the chemical recycling of fluoropolymers by bringing together diverse skills and resources
Supporting waste management strategies
Green Fluoropolymer Factory
R22-free production of fluoropolymers based on secondary raw materials
Gerdes 05/23