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Materials Science & Technology
Penetration of nano-sized metallic fuel additives from diesel vehicles
University of Applied SciencesBiel-Bienne, Switzerland
IC-Engines and Exhaust Gas Control
Matter Engineering AG
TTM Technik Thermische Maschinen
A. Ulrich, A. Wichser, N.V. Heeb, T. Mosimann, M. Kasper, J. Czerwinski, A. Mayer
Principle of a Particle Filter Systems (DPF)
2 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Endcaps
Soot Filtrationunfiltered exhaustparticulate matterfiltered exhaustsintered material
Emission Inlet: Soot, HC, CO, Metals,... Channel Wall
Emission ReleaseCO2, H2O
Endcaps
Soot Filtrationunfiltered exhaustparticulate matterfiltered exhaustsintered material
Emission Inlet: Soot, HC, CO, Metals,... Channel Wall
Endcaps
Soot Filtrationunfiltered exhaustparticulate matterfiltered exhaustsintered material
Emission Inlet: Soot, HC, CO, Metals,... Channel Wall
Emission ReleaseCO2, H2O
Effective reduction of particulates with DPFFiltration effectivity >99 %
3 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
1.0E+00
1.0E+02
1.0E+04
1.0E+06
1.0E+08
10 100 1000mobility diameter [nm]
#/cm
3 [d
N/d
log(
Dp)
]
w /o additiveFe+amineFe + amine / DPF
1. point
>3 orders of magnitude
High potential of diesel particle filtersEuro 3 + DPF versus Euro 4 and Euro 5 Poster 38
4 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008A.Mayer et al., Nanopartikel-Emissionen von HDV Euro 4 und Euro 5 Dieselmotoren im Vergleich zu Euro 3 mit/ohne Partikelfilter, 4.FAD-Konferenz „Herausforderung Abgasnachhandlung für Dieselmotoren“ Dresden 9.11.2006
Alptransit NEAT tunnel (57 km) -the longest rail way tunnel of the world
5 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
6 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0
100
200
300
400
vor 1998 1998-2000
2001 2002 2003 2004
Die
sel S
oot [µg
/m3 ]
Soot Reduction at tunnel construction sitesdue to diesel particle filters (DPF) SUVA 2004
760 µg/m3
1 Maximum working place concentration
MAK1
BG2
2 Background concentration
Overview DPF Systems with Online Regeneration
7 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
NOx PM
Continuous SCR selective catalytic reduction
CRT®
Continuously regeneration trap
Discontinuous NCA NOx catalytic adsorption
DPF FBC-DPF: diesel particle filter with fuel borne catalyst CSF-DPF: with catalytic coating
8 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0
20
40
60
80
100
0 5 10 15 20 25 30 35 40Time [min]
Con
vers
ion
[%]
Soot combustion dependent on temperaturedotted lines w/o catalytic support (additive)1
450 °C
500 °C
550 °C
600 °C650 °C
1Pierre Macaudiere et al. , AFS Conference 2003
Particle Filter System ConceptsMetal catalyzed combustion of collected soot
Fuel borne catalyst
9 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Catalytic coating
10 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Fuel borne catalystAddition of metal catalyst to fuel=> dosing concept / optimization
Catalyst in soot => catalyst in center of particulates=> higher efficiency of regeneration
Shorter regeneration time 4 min for 30g of soot (G. Belot 2003)
Always fresh catalyst
Hazard of penetration additive metals, nanoparticles => Increase during regeneration? DPF aging (cracks, ...)?
Hazard of precipitation / deposit(homogeneous mixture / mass balance)
Particle Filter System ConceptsMetal catalyzed combustion of collected soot
Catalytic coatingNo additional metal in fuel
Surface catalyst in coating=> direct contact necessary=> risk of incomplete regeneration
Longer regeneration time 20 min for 30g of soot (G. Belot 2003)
Possible aging of the catalyst
Hazard of abrasion lowerthan penetration (new DPF) => aging?
Hazard of accumulation => release; poisoning e.g. sulphur at Pt surfaces
Precipitation of a Fuel Additive
11 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
12 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Example for a Mass balance for Cerium -Total mass per cycle
0.96 µg/kWh0.2 µg/Nm³
Emissions factor
96.7 %98.2 %
99.94 %
Filtration rate in engineFiltration rate in trapTotal filtration rate system
457 mg15.1 mg0.27 mg
Deposition in engineDeposition in trapErmitted into ambient
15.37 mg0.27 mg
Total mass exhaust gas with trapTotal mass exhaust gas with trap
2.05 µg0.037 µg
Total mass ELPI without trapTotal mass ELPI with trap
473 mgAdditive quantityCerium
0.96 µg/kWh0.2 µg/Nm³
Emissions factor
96.7 %98.2 %
99.94 %
Filtration rate in engineFiltration rate in trapTotal filtration rate system
457 mg15.1 mg0.27 mg
Deposition in engineDeposition in trapErmitted into ambient
15.37 mg0.27 mg
Total mass exhaust gas with trapTotal mass exhaust gas with trap
2.05 µg0.037 µg
Total mass ELPI without trapTotal mass ELPI with trap
473 mgAdditive quantityCerium
, tank, etc.
A. Ulrich et al., Anal. Bioanal. Chem. 2003
Release of stored sulphur from Pt coated DPF at T > 400 °C => long term operation at low load conditions (VERT 2000 h operation test, S < 50 ppm) => PM filtration rate: particle No. >98 %, but bad particle mass=> Release time > 30 min
13 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Sample ID Set point n / M ∆m t5 t6 Amout of water loss
Cl NO2 NO3 PO4 SO4
[min-1 / Nm] [mg] [°C] [°C]LOD 0.03 0.03 0.03 0.03 0.03V21 2 1400/605 32.1 491 417 11.2 <DL <DL <DL <DL 6.0V22 2 1400/605 30.3 491 417 10.1 <DL <DL <DL <DL 5.2V23 6 1400/297 0.2 321 289 0 0.03 <DL 0.08 <DL 0.03V24 6 1400/297 0.4 321 289 0 0.03 <DL 0.05 <DL 0.2V25 5 2000/252 0.2 334 309 0 0.05 <DL 0.11 <DL 0.05V26 5 2000/252 0.4 334 309 0 <DL <DL 0.03 <DL 0.25V28 1 2000/530 5.4 481 430 0.8 <DL <DL <DL <DL 1.9V29 1 2000/530 6.1 481 430 0.9 <DL <DL <DL <DL 2.2V27 2 (Rep) 1400/600 19.9 501 418 5.9 <DL <DL <DL <DL 4.9V30 2 (Rep) 1400/600 18.4 501 418 5.3 <DL <DL <DL <DL 4.1
mg/filter
Sulphur ArtefactsCondensationA. Ulrich et al., 11. ETH Conference on Combustion Generated Nanoparticles 2007A. Mayer, A. Ulrich et al., SAE 2008-01-0332
Release time for stored SOx artefactsResults for DPF 7
14 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0
10
20
30
40
50
0 10 20 30 40Time [min]
∆m
[mg]
420
440
460
480
500
520
T [°
C]
Release time > 30 Min
higher T promote release
A. Ulrich et al., 11. ETH Conference on Combustion Generated Nanoparticles 2007A. Mayer, A. Ulrich et al., SAE 2008-01-0332
Release of stored sulphur from Pt coated DPF at high Temperature long term accumulation at low load condiitons
15 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0
10
20
30
40
V23 V24 V25 V26 V28 V29 V21 V22 V27 V30Sample ID
Mas
s in
mg
∆m [mg]Total water loss SO4 contribution
A. Ulrich et al., 11. ETH Conference on Combustion Generated Nanoparticles 2007A. Mayer, A. Ulrich et al., SAE 2008-01-0332
16 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Fuel borne catalystAddition of metal catalyst to fuel=> dosing concept / optimization
Catalyst in soot => catalyst in center of particulates=> higher efficiency of regeneration
Shorter regeneration time 4 min for 30g of soot (G. Belot 2003)
Always fresh catalyst
Hazard of penetration additive metals, nanoparticles => Increase during regeneration? DPF aging (cracks, ...)?
Hazard of precipitation / deposit(homogeneous mixture / mass balance)
Particle Filter System ConceptsMetal catalyzed combustion of collected soot
Catalytic coatingNo additional metal in fuel
Surface catalyst in coating=> direct contact necessary=> risk of incomplete regeneration
Longer regeneration time 20 min for 30g of soot (G. Belot 2003)
Possible aging of the catalyst
Hazard of abrasion lower than penetration (new DPF) => aging?
Hazard of accumulation => release; poisoning e.g. sulphur at Pt surfaces
VERT Procedures
Swiss National Standard
SNR 277205
17 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
VSET: Possible formation of - toxic secondary emissions- penetration of FBC metals- abrasion of metallic coating
VFT2: long term behaviour
18 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
100 %
0.15
0.15
0.15
0.150.10
0.10
0.10
0.10
5
6
7
84
3
2
1
60 %
100 %
75 %
50 %
10 %
Load
Idling IntermediateRPM
RPM
Torq
ueISO 8178/4 C1-cycle for construction site engines
N. Heeb, EMPA Report 167985
19 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Constant V
olume
Sam
pling CV
S
Air
Engine
T, p
Fuel supply
Partial DilutionTunnel
Air
Flow-proportional Sampling
catalyticDPF
VOC GC-FID
VOCOX LC-UV/VIS
PAH
n-PAH GC-HR-MS
PCDD/F
VGravimetry
ELPI
SMPS
NanoMet
ICP-MSMetals
V
V
Filter
PM Number/Surface
Sampling Parameter Methods
}Bag
Impinger
Dioxin Train
Mass
T, p
SizeDistribution
COCO2HCNONOxO2Opacity
NDIRNDIRFIDCLDCLDMagnosOpacity MeterM
ajor
com
pone
nts
Part
icul
ate
Mat
ter
Toxi
c tr
ace
com
pone
nts
Metals,Sulphur, Chlorine
ICP-MS, ICP-OES, XRF
Fuel
/ Lub
eoi
l
Constant V
olume
Sam
pling CV
S
Air
Engine
T, p
Fuel supply
Partial DilutionTunnel
Air
Flow-proportional Sampling
catalyticDPF
VOC GC-FID
VOCOX LC-UV/VIS
PAH
n-PAH GC-HR-MS
PCDD/F
VGravimetry
ELPI
SMPS
NanoMet
ICP-MSMetals
V
V
Filter
PM Number/Surface
Sampling Parameter Methods
}Bag
Impinger
Dioxin Train
Mass
T, p
SizeDistribution
COCO2HCNONOxO2Opacity
NDIRNDIRFIDCLDCLDMagnosOpacity MeterM
ajor
com
pone
nts
Part
icul
ate
Mat
ter
Toxi
c tr
ace
com
pone
nts
Metals,Sulphur, Chlorine
ICP-MS, ICP-OES, XRF
Fuel
/ Lub
eoi
l
VERT Sampling Procedures
Swiss National Standard
SNR 277205
20 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Principle of Electrical Low Pressure ImpactorELPI
Versorgung f.Hoch-Sp. & Ionenfalle
Elektrometer
A/D
Pumpe
Druck-Sensor
Reine Spühlluftfür Nullung
Corona Auflader
RS-232seriell
InternerRechner undSteuer-Elektronik
Externer PC, fürDaten-Speicherungund Bedienung
+5 kV
400 V
Abluft
LCD Anzeige undKontroll-Leuchten
+01E2
Vaquum-Pumpe
Eingang
Fluss-Kontrolle
Impaktor mitisolierten Stufen undKontaktstiften
Specification of ELPI impactor
21 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Stage Dso% [µm]
Di [µm]
Number min [1/cm3]
Mass min [µg/m3]
Mass max [mg/m3]
13 1012 6.8 8.4 8.00E+03 22 210011 4.4 5.3 2.00E+04 12 120010 2.5 3.2 4.00E+04 6.3 6309 1.6 2 8.00E+04 3.5 3508 1 1.3 2.00E+05 2 2007 0.65 0.81 3.00E+05 1 906 0.4 0.51 5.00E+05 0.4 405 0.26 0.33 9.00E+05 0.17 174 0.17 0.21 2.00E+06 0.078 7.83 0.108 0.15 3.00E+06 0.035 3.52 0.06 0.081 5.00E+06 0.015 1.51 0.03 0.042 9.00E+06 0.005 0.5
22 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Analysis Filter Samples
ICP-OES
ICP-MSeg. ELPI Filter
Sample Digestion Using Microwave
SEM/EDX
Characteristics of Plasma Mass Spectrometry ICP-MS
23 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
n Fast mulitelement technique 75 elements in 2 min.
n High sensitivity ppb to ppt levels (µg/L - ng/L)
n Large dynamic working range
n Fast scan => transient signals
n Resolution quadrupol-ICP-MS ~ 0.7 amuhigh resolution ICP-MS ~ 0. 001 amu
24 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Comparison of sensitivity and dynamic working range for different analytical techniques
X-ray techniques(XRF, PIXE, etc)
Types of fuel additives (FBC) Nanoparticulate (additive fuel suspension) versus organo-metallic additives (additive fuel mixture)
25 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Iron doped ceria
m
Ferrocene
~ 6 nm
Ferrocene
26 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0
20
40
60
80
100
0 5 10 15 20 25 30 35 40Time [min]
Con
vers
ion
[%]
Effect of a metal additive on soot combustiondotted lines w/o additive1 / solid line with Ce additive1 / Pt coating2
450 °C
500 °C550 °C
600 °C
450 °C
500 °C
550 °C
600 °C650 °C
1Pierre Macaudiere et al. , AFS Conference 20032K. Ogyu et al., 2006-01-1526
Pt coating 590 °C
27 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Effect of fuel additives on size distributionStandard Diesel 100 kW TDI Diesel Engine, 1400 rpm / 50 %Torque, SMPS
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
10 100 1000Dp [nm]
Part
icle
Num
ber C
onc.
dN
/dlo
g{D
p}[c
m-3
]
Standard
28 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Effect of fuel additives on size distributionStandard Diesel + 5 ppm Ceria Regeneration Additive 100 kW TDI Diesel Engine, 1400 rpm / 50 %Torque, SMPS
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
10 100 1000Dp [nm]
Part
icle
Num
ber C
onc.
dN
/dlo
g{D
p}[c
m-3
]
StandardAdd. 5 ppm
29 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Effect of fuel additives on size distributionStandard Diesel + 10 ppm Ceria Regeneration Additive 100 kW TDI Diesel Engine, 1400 rpm / 50 %Torque, SMPS
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
10 100 1000Dp [nm]
Part
icle
Num
ber C
onc.
dN
/dlo
g{D
p}[c
m-3
]
StandardAdd. 5 ppmAdd. 10 ppm
30 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Effect of fuel additives on size distributionStandard Diesel + 20 ppm Ceria Regeneration Additive 100 kW TDI Diesel Engine, 1400 rpm / 50 %Torque, SMPS
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
10 100 1000Dp [nm]
Part
icle
Num
ber C
onc.
dN
/dlo
g{D
p}[c
m-3
]
StandardAdd. 5 ppmAdd. 10 ppm Add. 20 ppm
31 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Effect of fuel additives on size distributionStandard Diesel + 35 ppm Ceria Regeneration Additive 100 kW TDI Diesel Engine, 1400 rpm / 50 %Torque, SMPS
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
10 100 1000Dp [nm]
Part
icle
Num
ber C
onc.
dN
/dlo
g{D
p}[c
m-3
]
StandardAdd. 5 ppmAdd. 10 ppm Add. 20 ppm Add. 35 ppm
32 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
10 100 1000mobility diameter [nm]
part
icle
num
ber c
onc.
dN
/dlo
g{D
p}[c
m-3
]
standardAdd. 35 ppm
add. part. soot part.
Effect of fuel additives on size distributionStandard Diesel + 35 ppm Ceria Regeneration Additive 100 kW TDI Diesel Engine, 1400 rpm / 50 %Torque, SMPS
Effect of fuel additives on size distribution5 ppm Fe + 31ppm C8 amine // 5 ppm Fe + 5 ppm Cu regeneration additives
33 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0.0E+00
1.0E+07
2.0E+07
3.0E+07
4.0E+07
5.0E+07
10 100 1000mobility diameter [nm]
#/cm
3 [d
N/d
log(
Dp)
]
w /o additive
Fe+amine
Fe + Cu
1. point
Effect of fuel additives on size distributioniron/amine and iron/copper regeneration additive
34 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0.0E+00
1.0E+07
2.0E+07
3.0E+07
4.0E+07
5.0E+07
10 100 1000mobility diameter [nm]
#/cm
3 [d
N/d
log(
Dp)
]
w /o additive
Fe+amine
Fe + Cu
5. point
Effective retention for FBC in the DPFFe/amine additive
35 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
1.0E+00
1.0E+02
1.0E+04
1.0E+06
1.0E+08
10 100 1000mobility diameter [nm]
#/cm
3 [d
N/d
log(
Dp)
]
w /o additiveFe+amineFe + amine / DPF
1. point
Fe penetration <0.8%emission factor 1.6 µg/Nm3
Effective retention for FBC in the DPF Filtration effectivity >99 %
36 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0.00001
0.00010
0.00100
0.01000
0.10000
10 100 1000mobility diameter [nm]
#/cm
3 [d
N/d
log(
Dp)
]
penetration, 1. point
Fe penetration <0.8%emission factor 1.6 µg/Nm3
Effective retention for FBC in the DPFFe/Cu additive
37 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
1.0E+00
1.0E+02
1.0E+04
1.0E+06
1.0E+08
10 100 1000mobility diameter [nm]
#/cm
3 [d
N/d
log(
Dp)
]
w /o additiveFe + CuFe + Cu / DPF
1. point
Cu penetration <0.1%emission factor 0.29 µg/Nm3
Effective retention for FBC in the DPFFe/Cu additive
38 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0.00001
0.00010
0.00100
0.01000
0.10000
10 100 1000mobility diameter [nm]
#/cm
3 [d
N/d
log(
Dp)
] penetration, 1. point
Cu penetration <0.1%emission factor 0.29 µg/Nm3
39 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
N. V. Heeb et al., Environ. Sci. Technol. 42 (10), 2008 3773 – 3779.D. Wenger et al., Environ. Sci. Technol. 42(8); 2008; 2992-2998.
Potential of DPF to reduce toxic componentse.g. PAHs / Toxicity Talk N.V. Heeb
Metall emissions determined by XRF Oxidation catalyst (OC) versus DPF with OC M. Gautam et al. Chemical characterization of PM emissions from a catalyzed trap equipped natural gas fueled transit bus, ETH Conference on Combustion Generated Nanoparticles 2007
40 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
<DL
for C
8.3G
+ w
ith D
PF
+ O
C
41 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Effect of metallic fuel additives on formation of secondary emissions e.g. Dioxin with Cu
N.V. Heeb, Environ. Sci. Technol.; 2007; 41(16); 5789-5794. N.V. Heeb et al., ETH Conference on Combustion Generated Nanoparticles 2007
Fe
Cu
Is there a difference in penetration of FBC during regeneration phase compared to
loading phase?
42 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
43 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Relative enhancement of emissions during DPF regeneration phase for a Fe/Cu additive
0
5
10
15
20
25
30
1 2 3 4 5 6 7 8 9 10 11 12ELPI Stage
rel.
emis
sion
of r
egen
erat
ion
vers
us lo
ad p
hase
Fe Reg/LoadCu Reg/Load
element and size dependent increase of penetration during
regeneration phase => depending on loading
status of the DPF
44 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Ce ( sampling raw gas ) Ce ( gravimetric filter )
conc
entra
tion
[mg/
km]
without regenerationwith regenerationweighted average
<D
L
Loading versus Regeneration phase Ceria Regeneration Additive – Possible Penetration of the Additive Metal Ce
45 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0
20
40
60
80
100
Zn ( sampling raw gas ) Zn ( gravimetric filter )
conc
entra
tion
[mg/
km]
without regenerationwith regenerationweighted average
Loading versus Regeneration Ceria Regeneration Additive – Possible Release of Stored Metals e.g. Zn
46 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
0
200
400
600
800
1000
Ca ( sampling raw gas ) Ca ( gravimetric filter )
conc
entra
tion
[mg/
km]
without regenerationwith regenerationweighted average
<DL
Loading versus Regeneration Ceria Regeneration Additive – Possible Release of Stored Metals e.g. Ca
Advantages and Disadvantages of DPF
47 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
High filtration efficiency for particle (> 99 % can be achieved)
Reduction of toxic and carcinogenic components e.g. PAHs, metals
Hazard of formation of secondary emissionCu (e.g. FBC) supports Dioxin formation, Pt coating tends to sulphur accumulation
Possible deposition of FBC in the engine (precipitation)
Fuel additive can change size distribution of emission
Enhanced penetration of FBC during regeneration phasedepending on the loading status of the DPF(penetration of catalytic metal additive and release of stored metals)
Contribution of penetration during regeneration is low when short regeneration time is taken into account(if DPF ageing effects further increase needs to be checked)
Outlook – Further Investigations
48 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Localization of additive deposition (engine, exhaust pipe, CVS)
Does an “initial deposition phenomenon exists? (later release?)
Long-term stability of additive fuel mixtures (Influence of additive and fuel composition, homogeneity of mixture, temperature stability)
Influence of lubricants
Further investigations on the DPF operation conditionsloading and regeneration phases (fuel additives, coating)
Retaining of metals in the DPF (possible release during regeneration?)
Storage and release effects (e.g. sulphur)
Long-term behaviour of DPF on penetration or abrasion (aging)
Comparison of different concepts (DPF + FBC; coated DPF)
Acknowledgements
49 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
Z. Stepien and S. Oleksiak (Additives) Institute of Petroleum Processing, Cracow/PolandJ. Czerwinski, P. Comte, J.L. Petermann, T. Neubert(Test stand) University of Applied Science BielT. Mosimann, A. Hess, M. Kasper (ELPI, SMPS) Matter EngineeringA. Wichser, U. Gfeller, N.V. Heeb, P. Schmid(Analysis) EmpaA. Mayer (Coordination)BAFU, SUVA, Industry Partners (Finance)
50 Materials Science & TechnologyEmpa, 12th Conference on Combustion Generated Nanoparticles 2008
June 7 – 29, 2008
Thank you for your attention