Document NGDx005x957xp5L5dnvJrgYww
Incineration of Fluoropolymers Project presentation
Dr. Hans-Joachim Gehrmann, Karlsruhe Institute of Technology (KIT) Sven Herremans, SGS Belgium NV
Dr. Philip Taylor, 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 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
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 Pro-K, Fluoropolymer processing and downstream user association, Germany Dr. Philip Taylor, P Taylor & Associates, LLC, USA Dr. Bruno Ameduri, Senior Researcher at ICGM, University of Montpellier, France Environmental Standards Inc., USA UBA, Umweltbundesamt (German Federal Environment Agency)
3
Test facility BRENDA / Sampling locations
Interior Rotary kiln
Thermal power
Overall 2.5 MW
Rotary kiln 1.5 MW
Post-combustion chamber 1 MW
Flue gas cleaning 17 BImSchV
The BRENDA plant is a large facility that is a good representation of commercial waste-to-energy plants in Europe
4
Test facility BRENDA / Post-combustion chamber -Triple T
PFAS Project, Level E1b
setting 1
setting 2
Start post combustion
zone [m] 1 meter above
7,65
7,65
the burners
Temperature in the post
combustion chamber
860
1100
(PCC) [C]
E2
3
Temperature,
Volume flow VPCC [mN /h
3947
3257
gas
E1b
wet] after boiler
PFAS
Cross section PCC [m2]
2,82
2,82
Volume flow VPCC [m3/h] Height h [m] level E1b
16.382 10,88
16.382 10,88
gas burner
Residence time from start 2,00 2,00 PCC zone to level E1b [s]
Wood chips / oil / gas burner
Rotary kiln
PFAS, gas measurement, HF (SICK-laser)
E2 gas sampling (+12.60 m)
E1b PFAS sampling (+10.88 m)
Start post-combustion zone (+7.65 m)
Burner level (+6.65 m)
0 m
5
Experimental Setup
test
number of HF and parameters PFAS sampling
start-up with natural gas and oil
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
oil, natural gas and 100
3
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. Pro-K 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 OTM-45 for sampling train 2. Combustion Ion Chromatography (CIC) for Adsorbable Organic Fluorine (AOF) 3. Ultrahigh-Performance Liquid Chromatography coupled to tandem Mass Spectrometer (UPLC-MS/MS) for targeted long
chain PFAS 4. Gas chromatography coupled to mass spectrometry (GC-MS) 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 OTM-45 sampling train
Thermocouple
Cerilrela or slac
Probe and tbnle
Temperature Readout
canister slot for volatile C1-04 compunds
failsafe XAD-2
Type Pitot Tube
ice Bath
Manometer
condensate impinger
water impinger Exnaus
SG modified PFAS sampling train
stack Gas Flow
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 Pre-run, Run and Post-run 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)
HF [mg/m3 wet*]
30
25
20
15
test of fluoropolymer
10 feeder
5
HF-SICK-Laser profile
p.
RUN 1
RUN 2
RUN 3
$
RUN 4
RUN 5
RUN 6
0 10 20 30 40 50 60 70
*with operational conditions: temperature boiler outlet 270 C,
80 90 100 110 120 130 140 150 160 170 180 6,2 Vol.-% (setting 1) and w2 = 8,5 Vol.-% (setting 2) Hours of operation
11
Fluorine balance (based on HF-Laser)
0,250 0,200
Preliminary results based on in-situ measuremnt of HF-concentration in flue gas by the means of HF-laser
F - input = 0,230 kg/h
Setting 1: T = 860C, t = 2s
0,182
RR = Recovery Rate [wt.-%]
Setting 2: T = 1100C, t = 2s
0,160
0,050
g
otr)l
I
d
CC
ii
CC
cc
cc
0,000
0,000
0,002
0,000
0,002
Set 1 / Run 1 / no F
Set 1 / Run 2 / F-feeding
Set 1 / Run 3 / no F
Set 2 / Run 4 / no F
Setting/ Run / Condition
Set 2 / Run 5 / F-feeding
Set 2 / Run 6 / no F
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 Non-detectable
Stack
Non-detectable
Non-detectable
Sum of PFAS (ng/m3) 1.5 0.3 5.1
TFA (LOQ - 14 g/m3) Non-detectable Non-detectable Non-detectable
13
Results from GC-MS 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/statistics-explained/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 long-chain PFAS were non-detectable at levels of < 1 ng/m3
PFAS analysis of wastewater and ash residue: A large majority of the samples were non-detectable with reporting limits of 0.02 g/l GC-MS analysis for short chain fluorocarbons: Non-detectable at a reporting limit of 5-30 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 waste-to-energy 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