Penetration of nano-sized metallic fuel additives from ... · Materials Science &Technology Penetration of nano-sized metallic fuel additives from diesel vehicles Unive rsit y of

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



Endcaps



Emission ReleaseCO2, H2O

Effective reduction of particulates with DPFFiltration effectivity >99 %


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



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


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


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


Catalytic coating

http://images.google.ch/imgres?imgurl=http://www.dieselnet.com/tech/images/cat/mat_washcoat.jpg&imgrefurl=http://www.dieselnet.com/tech/cat_mat.html&h=239&w=346&sz=32&hl=de&start=1&tbnid=L13H0K_4FtpQrM:&tbnh=83&tbnw=120&prev=/images%3Fq%3DSEM%2Bdiesel%2B%2Bparticle%2Bfilter%2Bplatinum%2Bcoating%26gbv%3D2%26hl%3Dde%26sa%3DG


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)


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



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


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


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


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


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)


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


VSET: Possible formation of - toxic secondary emissions- penetration of FBC metals- abrasion of metallic coating

VFT2: long term behaviour


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


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


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


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


Analysis Filter Samples

ICP-OES

ICP-MSeg. ELPI Filter

Sample Digestion Using Microwave

SEM/EDX

Characteristics of Plasma Mass Spectrometry ICP-MS


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


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)


Iron doped ceria

m

Ferrocene

~ 6 nm

Ferrocene

http://en.wikipedia.org/wiki/Image:Ferrocene_3d_model_2.png

http://de.wikipedia.org/wiki/Bild:Ferrocene.png


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


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


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



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



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



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


1.00E+05

1.00E+06

1.00E+07

1.00E+08

1.00E+09


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 distribution5 ppm Fe + 31ppm C8 amine // 5 ppm Fe + 5 ppm Cu regeneration additives


0.0E+00

1.0E+07

2.0E+07

3.0E+07

4.0E+07

5.0E+07


#/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


0.0E+00

1.0E+07

2.0E+07

3.0E+07

4.0E+07

5.0E+07


#/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


1.0E+00

1.0E+02

1.0E+04

1.0E+06

1.0E+08


#/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 %


0.00001

0.00010

0.00100

0.01000

0.10000


#/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


1.0E+00

1.0E+02

1.0E+04

1.0E+06

1.0E+08


#/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


0.00001

0.00010

0.00100

0.01000

0.10000


#/cm

3 [d

N/d

log(

Dp)

] penetration, 1. point

Cu penetration <0.1%emission factor 0.29 µg/Nm3


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


<DL

for C

8.3G

+ w

ith D

PF

+ O

C


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?



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


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


0

20

40

60

80

100

Zn ( sampling raw gas ) Zn ( gravimetric filter )

conc

entra

tion

[mg/

km]


Loading versus Regeneration Ceria Regeneration Additive – Possible Release of Stored Metals e.g. Zn


0

200

400

600

800

1000

Ca ( sampling raw gas ) Ca ( gravimetric filter )

conc

entra

tion

[mg/

km]


<DL

Loading versus Regeneration Ceria Regeneration Additive – Possible Release of Stored Metals e.g. Ca

Advantages and Disadvantages of DPF


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


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


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)


June 7 – 29, 2008

Thank you for your attention

Documents

Penetration of nano-sized metallic fuel additives from ... · Materials Science &Technology Penetration of nano-sized metallic fuel additives from diesel vehicles Unive rsit y of