Document LgZd697qvD0vowvVoGbdGD5Nd
Incineration of Fluoropolymers Project presentation
"III<s Karlsruhe Institute of Technology (KIT) com
BEEP Taylor & Associates, LLC
15th June 2023
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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
nN
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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
EE Taylor & Associates, LLC, USA
I
I
Environmental Standards Inc., USA
= <ity of Montpelier France
UBA, Umweltbundesamt (German Federal Environment Agency)
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Test facility BRENDA / Sampling locations
Fuel
3
Oil
Rotary
Kiln
Combustion Chamber
Air
8Q
Waste
Heat
Boiler
Spray
Drier
Process Steam
40 bar, 250 C
Fabric
Filter
(rl|
Adsorbent
Flue Gas Scrubber Scrubber 1 Scrubber2
L H,0
SCR Stack
Catalyst
Thermal power
nN 1
Ammonia Liquor
Rotary kiln
1.5 MW
Salts,
Flue Dust
Loaded Adsorben
O
Slag Boiler Ash
PFAS sampling fluegas SGS
|
PFAS Sampling residues & liquids (SGS)
Gas Burner
=
Induced
NaOH
Draught
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
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Test facility BRENDA/ Post-combustion chamber -Triple T
PFAS
Start post combustion zone [m] 1 meter above
the burners
Project, Level setting
7,65
E1b 1
Temperature in the post
combustion chamber
860
(PCC) [C]
3
Volume flow Vpce [my/h wet] after boiler
3947
Cross section PCC [m?] Volume flow Vpcc [m*/h]
Height h [m] level E1b
Residence time from start
PCC zone to level E1b [s]
2,82 16.382
10,88
200
setting 2 7,65
1100
3057 2,82 16.382 10,88 2,00
Wood chips / oil / gas
burner
PFAS, gas measurement, HF (SICK-laser)
(+10.88 m) Start post-combustion zone
om
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Experimental Setup
test
| parameters
number of HF and ooo samplin
start-up with natural gas and oil
"
:
"
starting solid feeding (wood chips)
background of rotary kiln / combustion chamber with
3 oil, natural gas and 100 kg/h wood chips
locations
| ' Ha ath solid fuel: woodchip (100
no
Top of post-
kg/h) + 320 g/h FP together TrFocec:: 860 C;:
mbusti
with oil and natural 9 gas
20s
chanmer
s
3
after boiler, stack
background of rotary kiln /
no
combustion chamber with
oil, natural gas and 100
kg/h wood chips
3
Change of temperature post combustion chamber
background of rotary kiln / combustion chamber with
2 oil, natural gas and wood chips
solid fuel: woodchip (100
no
kg/h) + 320 g/h FP together Tecc: 1100 } C;
with th oil oil and and natnuartuarlal gas
20s
3
Top of postcombustion
chamber (E1b), after boiler, stack
background of rotary kiln /
Wo
combustion chamber with
oil, natural gas and 100
kg/h wood chips
3
shut down
duration [hrs] 24 24
11
9 1" 13 1 12
hn
9 1 13 11 24
RUN
date / remarks 25.2.23; 10 a.m. 26.2.23; 10 a.m.
day 1 and 2
day
1
27.2.2023: 9 am
day 3
Monday
feeding of fluoropolymers vennio2ht
2
28.2.2023; 9 am
day 4
-
stop
feeding the
flouropolymers
in
evening
Tuesday
3
01.03.2023; 9 am
day 5 [Wednesday
over night
2
02.03.2028:3 9:am
day 6 | Thursday
go a feeding of fluoropolviymers
5
03.03.2023; 9 am
-
flouropolymers stop feeding in the evening
day 7
Friday
6
04.03.2023; 9 am
day 8 Saturday
day 9
Material
PTFE tubes
Mass fraction [Wt.-%] 63,00
PTFE tape
PVDF
7,00 18,00
PFA
6,00
FKM rubber
6,00
mass flow = 320 g/h
Basis of fluoropolymer feed mixture:
1. Feed mixture comprises of4 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
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Main Operational Parameters, Setting 1 and 2
mass flow wood chips
main air
13 mass flow heating oil
X
|volume flow natural gas
volume flow combustion air
2E inclination
rotation speed
temperature flue gas outlet
thermal power
unit
kg/h
my'/h
kg/h
my'/h my*/h
rev p.m C MW
setting S1 RUN1,2,3
98
setting S2
| RUN4,5,6
98
418
423
61
46
4
4
872
753
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
volume flow natural gas to burner D4.1
"
2
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
22 temperature flue gas post-combustion chamber outlet (with control)
[CO (level E2)
8 |0, (level E2)
thermal power
total thermal power rotary kiln and post combustion chamber
-- |volume flow
HS] > 0, 52 [co
water vapour
my'/h my/h my'/h my'/h
s
C
mg/m'
Vol.-% dry
MW MW
my'/h
Vol.-% dry
mg/m
Vol.-% wet
22 671 22 671
860 0.2 1.2 0.46 1.59
3958 11.9 1.35 6.20
35 429 35 428
1095 1.2 7.0 0.72 1.67
3238 9.0 1.64 8.49
Increase of temperature by reduction of
stochiometric ratio
+ 260 kW = constant
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PFAS analysis
Modified OTM-45 for sampling train Combustion lon Chromatography (CIC) for Adsorbable Organic Fluorine (AOF) Ultrahigh-Performance Liquid Chromatography coupled to tandem Mass Spectrometer (UPLC-MS/MS) for targeted long
chain PFAS
Gas chromatography coupled to mass spectrometry (GC-MS) for volatile Fluorocarbons lon chromatography (IC) for Trifluoroacetic Acid (TFA) lon Selective Electrode (ISE) for Inorganic Fluoride Tunable Diode laser for Hydrogen fluoride
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Modified OTM-45 sampling train
Thermocouple
Temperature Readout
canister slot for volatile C1-C4 compunds
failsafe XAD-2
Tv) Fitot Tube
Ice Bat
ol
35380:
V
.
Manome! ter
condensate impinger
water impinger
Stack Gas Flow
SGS modified PFAS sampling train
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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
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HF measurement after the boiler (Tunable Diode Laser)
30
25
nN o
wet*]
[mg/m? -[4,}
HF
-o
test of
fluoropolymer
feeder
&
LJ
Ld
N
HF-SICK-Laser profile
Lad
< Pode %
om.
io
a
Ld
LJ
LJ
LJ
LK
av J >
$
1)
id
eo LJ
RUN 1 Fi
RUN 2
RUN 3
$
:
s
RUN 4
LJ
RUN 5
3
*
RUN 6
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
*with operational conditions: temperature boiler outlet 270 C, w, = 6,2 Vol.-% (setting 1) and w, = 8,5 Vol.-% (setting 2) Hours of operation
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Fluorine balance (based on HF-Laser)
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
0,200
Setting 1: T=860C, t = 2s 0,182
RR = Recovery Rate [wt.-%] Setting 2: T=1100C, t= 2s
[kg/h] 0,150
0,160
output
Total
Fluorine
79,03%
=
RR
1,09%
0,69%
=
RR
=
RR
0,000
0,002
0,000
I=] I<] ~
Set1/Runl/noF
Set 1/ Run 2 / F-feeding
Set1/Run3/noF
Set2/Run4/noF
Setting / Run / Condition
Set2/Run5/F-feeding
Set2/Run6/noF
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Summary of analytical results (860C)
Post combustion
Avg. Total Fluorine
(mg/m')
2
(LOQ (gas) = 27 ug/m'),
(LoQ (part) -- 1.7 pg/m')
36.5
Avg. AOF ,
(LOQ- 27 pg/m')
31.5
After Boiler
17.3
Non-detectable
Stack
Non-detectable
Non-detectable
Sum of PFAS (ng/m")
4.5 0.3
TFA
;
(LOQ-14 pg/m')
Non-detectable
Non-detectable
Non-detectable
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Results from GC-MS analysis (50 samples)
Short chain fluorocarbons Tetrafluoromethane Hexafluoroethane
Trifluoromethane
Hexafluoropropylene
Pentafluoroethane
Octafluorocyclobutane
LOQ (pg/m3)
20 30 20 5 25 25
Results (Stack)
Non detectable except 2 values in separate runs near
detection limits (20, 27 ug/m3)
Non detectable
Non detectable
Non detectable
Non detectable
Non detectable
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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 ,., 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 4,
= 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
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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 ug/m?
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 pg/I
GC-MS analysis for short chain fluorocarbons: Non-detectable at a reporting limit of 5-30 pg/m? levels
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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
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Thhaannkk yyoouu
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