influence of ash-forming gasoline additives such as mmt ... action/fuel_quality... · influence of...

Influence of Ash-Forming Gasoline Additivessuch as MMT® on Exhaust Emissions and Per-

formance Characteristics of PC-Engines

Brussels, July 14, 2005

Dr. Herwig RichterDr. Ing. h.c. F. Porsche AG, Adv. Powertrain Engineering EAV

22MMT- Fuel Additive

MMT® ... Methylcyclopentadienyl-Manganese-Tricarbonyl(CH3 - C5H4)Mn(CO)3Molecular-Weight … 218,086Manganese … 54,94 (Share 25,19 mass%)

Additive to increase knock-resistance of gasoline (as replacement for lead);Used in S-Africa, China, Canada; E-Europe too;

Forming deposits in the combustion chamber, on the Lambda-Sensors and on the catalysts (Manganese-oxides MnO2, Mn3O4):

- Increase of exhaust emissions- Loss of engine performance

33

MMT- Fuel Additive:Motivation, Objective

Joint investigation by AUDI, BMW, DC, Porsche und VW

to demonstrate the influence of MMT- additivated fuel on engine performance and exhaust emissions in comparison with standard fuel (Super-Plus) under defined European conditions;

44

Bench-Ageings over 179 hours with 2 engines Porsche Carrera 3,6 (EU-version, MT, MJ 04) including exhaust-systems (catalysts and Lambda-sensors):

Engine A: Super-PlusEngine B: Super-Plus with MMT® (15 mgMn/ltr ^ 20mgMn/kg)

Ageing Cycle

179 Hours (6400 ltr. Fuel) ~ 58.000 km

MMT- Fuel Additive:Procedure

10 Min 10 Min 10 Min 30 Min

~ 310 °C

2000 rpm, 57 Nm/2 bartExhaust ~ 350 °C

3000 rpm, 172 Nm/6 bartExhaust ~ 640 °C

tExhaust ~ 910 °C

1 Hour10 min 10 min 10 min 30 min

IdletExhaust

6000 rpm, 258 Nm/9 bar

6th gearspeed 245 kphupgrade 1 %

5th gear speed100 kphaccel. 0,8 m/s2

4th gearspeed 55 kphaccel. 0,3 m/s2

55MMT- Fuel Additive:

Fuel Specifications

Super-Plus Super-Plus withMMT

Test Method Analysis AnalysisCriterion Unit Nr. 1638 Nr. 1583

ROZ ... EN 25164: 1993 99.8 100.0MOZ ... EN 25163: 1993 88.0 88.2Density at 15 °C [kg/l] ISO 3675 0.7514 0.7687Vapour Pressure [kPa] prEN 13016-1: 1997 59.3 58.2up to 70 °C [%] prEN ISO 3405: 1998 30 26up to 100 °C [%] prEN ISO 3405: 1998 54 50up to 150 °C [%] prEN ISO 3405: 1998 87 84up to 180 °C** [%] prEN ISO 3405: 1998 97 97Final Boiling Point [°C] prEN ISO 3405: 1998 196 196Destillation Residue [Vol.%] prEN ISO 3405: 1998 1.0 1.2S-Content [mg/kg] EN ISO 14596: 1998 2.7 11.6Pb-Content [mg/l] EN 237: 1996 0.0 0.0Mn-Content [mg/kg] RFA 0 20.2Olefins [Vol.%] ASTM D 1319: 1995 4.9 4.7Aromatics [Vol.%] ASTM D 1319: 1995 32.3 39.8Paraffins [Vol.%] ASTM D 1319: 1995 49.9 40.5Benzene [Vol.%] EN 12177: 1998 0.75 0.78Ethers (mit C5) MTBE [Vol.%] EN 1601: 1997 12.9 15.0Total O-Content [Gew.%] EN 1601: 1997 2.36 2.63

Calculatetd Values:Lower Heat Value [MJ/kg] ASTM D 3338 41.758 41.303CWF ... ASTM 3343 0.849 0.853C : H : O ... ... 84,92:12,76:2,31 85,25:12,12:2,63HCV/OCV/WCV 1,791:0,020:0,000 1,694:0,023:0,000Ls 14.0 13.9









66

Measurements after 10 hours break-in and after 179 Hours ageing:• WOT-Performance• Exhaust emissions according EU test procedure

on the dynamic engine dynamometer and with a test vehicle Porsche Carrera on the emission rolls

• Oxygen storage capacity of the catalysts (OSC);

Additional tests after 100 hours ageing:• WOT-Performance• Exhaust emissions according EU test procedure

on the dynamic engine dynamometer •Oxygen storage capacity of the catalysts (OSC);

Break-in, WOT- and emission-tests have been performed on both engines with fuel Super-Plus, emissions-tests on the rolls with EU-4 Reference-fuel.

MMT- Fuel Additive: Test-Plan

77

MMT- Fuel Additive: Test-Engines Porsche Carrera

88

MMT- Fuel Additive: WOT-Results

150

200

250

300

350

400

1000 2000 3000 4000 5000 6000 7000

Engine Speed n [rpm]

Cor

r. To

rque

Md

[Nm

]

0

50

100

150

200

250

Cor

r. P

ower

Pe

[kW

]

after break-inafter 100 hrsafter 179 hrs

Engine "B": 66411563MMT

Pe

Md

150

200

250

300

350

400

1000 2000 3000 4000 5000 6000 7000


Cor

r. To

rque

[Nm

]

0

50

100

150

200

250

Cor

r. P

ower

Pe

[kW

]


Engine "A": 66411565Super-Plus

Pe

Md

150

200

250

300

350

400

1000 2000 3000 4000 5000 6000 7000Engine Speed n [rpm]

Cor

r. To

rque

Md

[Nm

]

0

50

100

150

200

250

Cor

r. P

ower

Pe

[kW

]



Pe

Md

150

200

250

300

350

400

1000 2000 3000 4000 5000 6000 7000Engine Speed n [rpm]

Cor

r. To

rque

Md

[Nm

]

0

50

100

150

200

250

Cor

r. P

ower

Pe

[kW

]



Pe

Md

150

200

250

300

350

400

1000 2000 3000 4000 5000 6000 7000


Cor

r. To

rque

[Nm

]

0

50

100

150

200

250

Cor

r. P

ower

Pe

[kW

]



Pe

Md

99


378 372 373237 233 234

150

200

250

300

350

400

after break-in after 100 hrs after 179 hrs

Max

. Cor

r. To

rque

Md,

max

[Nm

]

0

50

100

150

200

250

Max

. red

. Lei

stun

g [k

W]

Md,max Pe,max


378371

362

237229

223

150

200

250

300

350

400


Max

. red

. Dre

hmom

ent [

Nm

]

0

50

100

150

200

250

Max

. Cor

r. P

ower

Pe,

max

[kW

]

Md,max Pe,max


5 % Loss of max. Power3 % Loss of max. Torque

378 372 373237 233 234

150

200

250

300

350

400


Max

. Cor

r. To

rque

Md,

max

[Nm

]

0

50

100

150

200

250

Max

. red

. Lei

stun

g [k

W]

Md,max Pe,max


378371

362

237229

223

150

200

250

300

350

400


Max

. red

. Dre

hmom

ent [

Nm

]

0

50

100

150

200

250

Max

. Cor

r. P

ower

Pe,

max

[kW

]

Md,max Pe,max


5 % Loss of max. Power3 % Loss of max. Torque

1010


304 310 317

0

50

100

150

200

250

300

350

400


Exh

aus

Gas

Bac

k P

ress

ure

p3 [m

bar]

at n

= 6

850

rpm Engine "A": 66411565

Super-Plus

296

322336

0

50

100

150

200

250

300

350

400


Abg

asge

gend

ruck

p3

bei n

= 6

850

1/m

in [m

bar]


6 % Increase of Exhaust Gas Back Pressure at Rated Speed

304 310 317

0

50

100

150

200

250

300

350

400


Exh

aus

Gas

Bac

k P

ress

ure

p3 [m

bar]

at n

= 6

850

rpm Engine "A": 66411565

Super-Plus

296

322336

0

50

100

150

200

250

300

350

400


Abg

asge

gend

ruck

p3

bei n

= 6

850

1/m

in [m

bar]


6 % Increase of Exhaust Gas Back Pressure at Rated Speed

1111


200

225

250

275

300

325

350

375

400

1000 2000 3000 4000 5000 6000 7000


Spe

z. K

rafts

toffv

erbr

auch

be

[g/k

Wh]


200

225

250

275

300

325

350

375

400

1000 2000 3000 4000 5000 6000 7000


Spe

c. F

uel C

onsu

mpt

ion

bsfc

[g/

kWh]



Brake Spec. Fuel Consumtionup to 5 % higher

200

225

250

275

300

325

350

375

400

1000 2000 3000 4000 5000 6000 7000


Spe

z. K

rafts

toffv

erbr

auch

be

[g/k

Wh]


200

225

250

275

300

325

350

375

400

1000 2000 3000 4000 5000 6000 7000


Spe

c. F

uel C

onsu

mpt

ion

bsfc

[g/

kWh]



200

225

250

275

300

325

350

375

400

1000 2000 3000 4000 5000 6000 7000


Spe

z. K

rafts

toffv

erbr

auch

be

[g/k

Wh]


200

225

250

275

300

325

350

375

400

1000 2000 3000 4000 5000 6000 7000


Spe

z. K

rafts

toffv

erbr

auch

be

[g/k

Wh]


200

225

250

275

300

325

350

375

400

1000 2000 3000 4000 5000 6000 7000


Spe

c. F

uel C

onsu

mpt

ion

bsfc

[g/

kWh]



Brake Spec. Fuel Consumtionup to 5 % higher

1212

MMT- Fuel Additive: EU-Emission Tests(Dynamic Engine Test Bench)

0.36 0.36

0.60

0.790.82

0.54

0.04 0.04

0.060.07

0.040.05 0.05 0.04

0.06 0.06

0.11

0.07

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

SPlus MMT SPlus MMT SPlus MMT

CO

-Em

issi

ons

[ g/k

m ]

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

HC

-, N

Ox-

Em

issi

ons

[ g/k

m ]

CO HC NOx

Limit EU-4: 0,1 gHC/km

Limit EU-4: 1,0 gCO/km

Limit EU-4: 0.08 gNOx/km

after break-in 100 Hours 179 Hours

HC-Limit EU-4exceeded

1313

MMT- Fuel Additive: EU-Emission Tests(Cumulated HC-Emissions)

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0 100 200 300 400 500 600 700 800 900 1000 1100 1200Time [ s ]

Acc

um. H

C-E

mis

sion

s [

g/km

]

0

20

40

60

80

100

120

140

160

Spe

ed [

km/h

]

S-Plus, after break-in S-Plus, 179 HoursMMT, after break-in MMT, 179 HrsSpeed

1414

0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

2.50

0 100 200 300 400 500 600 700 800 900 1000 1100 1200

Time [ s ]

Acc

um. H

C-E

mis

sion

s/E

ngin

e-ou

t [g

/km

]

0

20

40

60

80

100

120

140

160

180

200

Spe

ed [

km/h

]

S-Plus, after break-in S-Plus, 179 HoursMMT, after break-in MMT, 179 HrsSpeed

HC- Emissions/Engine-out 30 % higher

MMT- Fuel Additive: EU-Emission Tests(Cumulated HC-Emissions/Engine-out)

1515

MMT- Fuel Additive: Test Vehicle on the Emission Rolls

1616

0.38 0.36 0.47 0.53 0.70

0.043 0.047

0.0680.075

0.030 0.0310.040 0.045

0.036

0.113

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

SPlus MMT SPlus MMT MMT

CO

-Em

issi

ons

[ g/k

m ]

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

HC

-, N

Ox-

Emis

sion

s [ g

/km

]

CO HC NOx

Limit EU-4: 0,1 gHC/km

Limit EU-4: 1,0 gCO/km

Limit EU-4: 0.08 gNOx/km

after break-in 179 Hours

179 Hours

Cat.SPlus

Cat.MMT

Cat.SPlus

Cat.MMT

Cat.+EngineMMT

HC-Limit EU-4exceeded

MMT- Fuel Additive: EU-Emission Tests(Emission Rolls

1717

MMT- Fuel Additive: Deposits in theCombustion Chambers

Super-Plus

Super-Plus with MMT

1818

MMT®- Fuel Additive: Deposits on the Spark Plugs

Super-Plus with MMT

Super-Plus

1919MMT- Fuel Additive: Deposits

on the Catalysts (1st Brick)

Super-Plus with MMT Super-Plus


Catalyst Performance Light-Off

0

20

40

60

80

100

250 270 290 310 330 350 370 390 410 430 450Exhaust Gas Temperature in Front of Catalyst [°C]

HC

-Con

vers

ion

Rat

e [%

]

S-Plus MMT

0

20

40

60

80

100

250 270 290 310 330 350 370 390 410 430 450

Exhaust Gas Temperature in Front of Catalyst [°C]

HC

-Con

vers

ion

Rat

e [%

]S-Plus MMT

1st Brick

2nd Brick

A/F ratio = 0,998air flow 125 kg/h


Catalyst Performance Lambda-Scan

0

20

40

60

80

100

0.98 0.985 0.99 0.995 1 1.005 1.01Air-Fuel ratio Lambda [1]

HC

-Con

vers

ion

Rat

e [%

]

S-Plus MMT

0

20

40

60

80

100

0.98 0.985 0.99 0.995 1 1.005 1.01

Air-Fuel Ratio Lambda [1]

Con

vers

ion

Rat

e [%

]

S-Plus MMTCO

NOx

1st Brick

air flow 125 kg/ht,exhaust gas = 450 °CLambda-amplitude +/- 4%

2222

MMT®- Fuel Additive: Lambda-Sensors

Super-Plus

Super-Plus with MMT

pre cat. behind 1st brick

pre cat.

behind 1st brick

2323

MMT®- Fuel Additive: Results (1)

After 179 hours bench-ageing ( ^ ~ 58.000 km) with MMT-additivated fuel (15 mgMn/ltr) in comparison to operation with Super-Plus fuel:

• 5 % loss of max. power output• 3 % loss of max. torque• 6 % increase of exhaust gas backpressure• 5 % increase of specific fuel consumption

Exhaust Emissions have been measured on the dynamic engine test benchand on the emission rolls according EU test procedure:• HC-Emissios increase by 54 % and exeed EU-4 limit

(Engine-out emissions increase by ~30 %)• CO-Emissions similar• NOx-Emissions increase by 14 %

2424

MMT®- Fuel Additive: Results (2)

Engine evaluation:

• Manganese oxide deposits in the combustion chambers and in the exhaustsystem;

• strong manganese oxide deposits impair the reliability of the spark plugs;• catalyst function is deteriorated by manganese oxide deposits during both

light-off and exhaust-gas conversion in warmed-up condition;• the oxygen sensors were fully operable;• the wear patterns were essentially the same;

These investigations have proved that use of MMT-additive in gasolinecauses harmful side effects.

influence of ash-forming gasoline additives such as mmt ... action/fuel_quality... · influence of...

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