Download - Coburg University of Applied Sciences and Arts · Coburg University of Applied Sciences and Arts . Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013 . Jürgen Krahl

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Picture: EXPO Aust, Bamberg

Coburg University of Applied Sciences and Arts


Jürgen Krahl Olaf Schröder Axel Munack Barbara Fey

Lasse Schmidt Kevin Schaper Jürgen Bünger

Emission and Health Effects from Biofuels


www.fuels-jrg.de


Introduction

Fuels, Engines, Methods

Results

Summary and Conclusions

Outline


0

50

100

150

200

250

3001000 h

ECE R49

ESC

FTP-75

HWY

JC08

ECE R83

UDDS

C1 Cycle

CFR T40 P86 SpN

JE05

JMEC

MVEG-A

NEDC

TMG2

TMG5

[%] relative to DF

HC CO NOx PM

Regulated Emissions from Biodiesel versus DF


Including different species of biodiesel * -50

-40

-30

-20

-10

0

10

20

HC CO NOx PMNOx

[%] relative to DF

Regulated Emissions from Biodiesel versus DF


0

5

10

15

0 20 40 60 80 100 Blend [% RME]

Em

issi

on [g

/h]

NOx

HC

CO

Farymann engine with catalytic converter, 5-mode test

NOx, HC und CO emissions of a single cylinder engine


Regulated Emissions from Fischer-Tropsch Fuels and Blends versus DF

0

50

100

150

200

250

300

350

400 13-modeARTEMISCBDCEC ModeESCETCFTPFTP-75FTP Cold StartFTP Hot StartHFETHWYISO 8710JC08JE05JMECLight-duty european test cycleNEDCTMG2TMG5US06WVU-5

HC CO NOx PM

[%] relative to DF

including different blends with diesel fuel *

* GtL-blends with diesel fuel (5 – 80 vol%)


Regulated Emissions from Fischer-Tropsch Fuels and Blends versus DF

-35

-30

-25

-20

-15

-10

-5

0

HC CO NOx PMNOx

[%] relative to DF


Components of Diesel Engine Emissions (DEE)

DEE consist of a complex mixture of compounds. Several can be hazardous to human health:

• Carbon monoxide (CO) • Carbon dioxide (CO2) • Sulfur dioxide (SO2) • Nitrogen oxides (NOX) • Hydrocarbons (HC), thereof ca. 2-5% • Polycyclic aromatic Hydrocarbons (PAH) • Particles

Source: HEI 1995


Carcinogenicity of DEE

Diesel engine emissions (DEE) are considered to be carcinogenic on the basis of numerous scientific data:

1. Strong mutagenicity of particle extracts of DEE in the Ames-test (Huisingh et al. 1978)

2. Lung tumors in rats after inhalation of DEE (Heinrich et al. 1986)

3. Increased lung cancer risk in occupationally DEE-exposed subjects (IARC 2012)

“In conclusion, the Working Group classified diesel engine exhaust as “carcinogenic to humans” (Group 1).”


Genotoxicity of diesel engine particles

(PAH)

Modified according to HEI 1995


Direct genotoxic mechanism:

Indirect genotoxic mechanism:

PAH: Modes-of-Action

DNA

DNA-Strand Breaks Mutations

H O

O H

O

B [ a ] P - 7 , 8 - d i h y d r o d i o l - 9 , 1 0 - e p o x i de

Reactive Oxygen Species (ROS) DNA-Oxidation

Mutations H O

O H

B [ a ] P - 7 , 8 - d i h y d r o d i o l

O

O

B [ a ] P - 7 , 8 - d i o ne


Non substituted PAH indirectly mutagenic Substituted PAH especially Nitro-PAH directly mutagenic

Carcinogenic Components of DEE

Benzo[a]pyrene

Nitro-benzo[a]pyrene

Often much stronger mutagenic!


Introduction


Results


Outline


Data Base

Projects: 23 studies from 1993 until 2012 Engines: 6 passenger cars, Euro 2 - 6;

7 truck engines, Euro 0 – VI; 2 one-cyl.-test engines (Euro 0)

Fuels: DF from gas stations and reference diesel fuel:

11 fossil (sulfur 2 - 500 ppm, aromatics 1 - 37%) 14 biogenic (sulfur <2 ppm, aromatics <1%)

Aftertreatment: Diesel Oxidation Catalyst (DOC)

Diesel Particle Filter (DPF) Selective Catalytic Reduction (SCR)


Cartridge KI-

Engine and Emission Laboratory


Sampling Setup for Mutagenicity Testing (according to VDI-guideline 3872, page 1)


0

500

1000

1500

2000

2500

3000

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Zeit [min]

Dre

hzah

l [1/

min

], D

rehm

omen

t [N

m]

0

50

100

150

200

250

Leis

tung

[kW

]

Drehmoment Bremse Drehzahl Motor Leistung

Torque brake Revolutions engine Power

Time [min]

Pow

er [k

W]

3000

2500

2000

1500

1000

500

0

250

200

150

100

50

0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Num

ber o

f Rev

olut

ions

[1/m

in],

Torq

ue [N

m]

Sampling during the ESC Test


0

500

1000

1500

2000

2500

3000

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Zeit [min]

Dre

hzah

l [1/

min

], D

rehm

omen

t [N

m]

0

50

100

150

200

250

Leis

tung

[kW

]

Drehmoment Bremse Drehzahl Motor Leistung

Num

ber o

f Rev

olut

ions

[1/m

in],

Torq

ue [N

m] 3000

2500

2000

1500

1000

500

0

Torque brake Revolutions engine Power

Time [min] 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Pow

er [k

W]

250

200

150

100

50

0

Sampling Conditions for Mutagenicity Testing


Sampling Setup for Mutagenicity Testing (according to VDI-guideline 3872, page 1)


Preparation of Test Solutions

Particle phase Soxhlet extraction of filters Dichloromethane (150 mL) Reduction by evaporation Drying under a stream of nitrogen.

Condensates Reduction by evaporation. Drying under a stream of nitrogen.

Re-dissolution of residues in 4 mL dimethyl sulfoxide (DMSO)


Bacterial Reverse Mutation Test = Ames-Test (OECD-Guideline 471)

Standard test protocol of Maron and Ames (1983) Mutat Res 113: 173-215 Tester strains TA98 and TA100 with and without metabolic activation by a microsomal rat liver enzyme fraction (S9) 4 concentrations; controls: DMSO (neg.) 3-NBA, 2-AF, MMS (pos.)

Docherty et al. Green Chem., 2006, 8, 560


Introduction


Results


Outline


Mutagenicity from VO, RME, and high sulfur DF Deutz Tractor, EURO < 0

0

250

500

750

1000

1250

1500

DF VO RME

Mut

atio

ns p

er P

late

TA98 -S9

TA98 +S91994


Mutagenicity of DF with high sulfur and optimization of RME combustion (Euro III)

0

100

200

300

400

500

600

idling 25% load rated power max. torque

Mut

atio

ns p

er p

late

DF without S9

DF with S9

RME without S9

RME with S9

RME opt. without S9

RME opt. with S9

2000


DF RME GTL 1 GTL 20

25

50

75

100

125

150

175

200

225

250

Fuels

Mut

atio

ns p

er p

late

Mutagenicity of LSDF, RME and GTL Truck Truck engine OM 904, Euro II

2004

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013 29

Mutagenicity of rapeseed oil Truck engine OM 904, Euro III

DF GTL RME VO 0

200

400

600

TA98-S9

TA98+S9

Mut

atio

ns

2007


Frequently Asked Questions

(...)

Why haven´t you done it earlier?

Who is responsible?

Am I endangered?

Endangeres me my boss or

my neighbour?

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013 31

VO_mod. DF GTL RME VO

Mut

atio

ns

0

200

400

600

800

1000

1200

1400

1600

TA98-S9

TA98+S9

2007

Mutagenicity of preheated rapeseed oil and viscosity improver


0

50

100

150

200

DF JME NExBTL RME

Mut

atio

ns [-

]

-S9+S9

0

50

100

150

200

DF JME NExBTL RME

Mut

atio

ns [-

]

Mutagenicity of PM-Extracts and Condensates Truck engine OM 906, Euro III

2008 Particulate Matter Condensate


-10

-5

0

5

10

15

20

25

Mut

atio

ns p

er p

late

DF cold

DF

HVOB7

HVOB7

DF

DF

HVOB

HVOB7 warm

DF

DF warm

HVOB

HVOB7 warm

Euro 6 Euro 5 Euro 3

Mutagenicity of Passenger Cars (2011)


0

5

10

15

0 20 40 60 80 100 Blend [% RME]

Em

issi

on [g

/h]

NOx

HC

CO

Farymann engine with catalytic converter, 5-mode test

NOx, HC und CO emissions of a single cylinder engine


0

50

100

150

200

250

300

GTL 1 GTL 2 DF B20 RME Fuels

Mut

atio

ns p

er p

late

TA98-S9 TA98+S9

Mutagenicity of Particulate Trick engine OM 906, Euro III


0

50

100

150

200

250

300

DF V-Power Ultimate B 20 V-P B 20 ULT RME Fuels

Mut

atio

ns p

er p

late

TA98-S9 TA98+S9

Mutagenicity of Particulate Trick engine OM 906, Euro III


0

20

40

60

80

100

DF B5 B10 B20 B50 RME Fuels

Mut

atio

ns p

er P

late

TA98-S9 TA98+S9

Mutagenicity of Particulate Test Engine AVL 502.019, rated power


0

20

40

60

80

100

DF B5 B10 B20 B30 B40 Fuels

Mut

atio

nen

per p

late

TA98-S9 TA98+S9

Mutagenicity of Particulate Truck Engine MAN D08, Euro IV


Deposits of oligomers

Biodiesel blends after nine weeks of natural aging


0

20

40

60

80

100

120

140

160

0 10 20 30 40 50 60 70 80 90 100oxidized RME in GtL [Vol %]

inso

lubl

e ol

igom

ers

[mg/

100

g]Deposits in GtL-biodiesel blends (after thermooxidation of biodiesel)


Artificial aging procedure

Air

RME

Thermooxidation

• T = 110 °C

• discharge of ambient air

• 40 h

Heating mantle


Formation of deposits


O2 O2

Source: Fang and McCormick, 2006 SAE Paper 2006-01-3300

. . . . . . 11

. . . . . . 11 14

9 10 12 13 15 16

. . . . . . 14

16

. . . . . . 16

O O

. . . . . .

O

. . . . . .

. . . . . . or O-O linkages

. . . . . . 11 13 15

O O

. . . . . .

. . .

O O

. . . 13 15

11 11

Probable mechanism of oligomerization


Dimer R2O6

COOCH3

O O

COOCH3

Trimer R3O10

O O COOCH3

COOCH3

O O

COOCH3

Aldol Dimer R'2O5 (R' < R)

COOCH3

C

O

COOCH3

Aldol Oligomer R'2RO9

COOCH3

O O C O

COOCH3

COOCH3

Source: Fang and McCormick, 2006 SAE Paper 2006-01-3300

Probable mechanism of oligomerization


Solution of deposits


Introduction


Results


Outline


Reduction of Mutagenicity over Two Decades

No significant mutagenicity: • Euro 5 and 6 passenger cars • Euro VI trucks (not shown)

0

100

200

300

400

500

Fossil fuels Biogenic fuels

Mut

atio

ns p

er L

Exh

aust


Conclusions

• Mutagenicity of DEE was lowered to non significant levels in the last 20 years using the Ames test.

• Regulated components do not indicate health effects from diesel engines.

• Independent fuel research is needed for a sound and reliable consumer and worker protection.


Working Group 2013


Thank you for your kind attention!

[email protected]