Influence of Ash-Forming Gasoline Additives such as MMT ... action/fuel_quality... · Influence of...
Transcript of 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
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
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
Engine Speed n [rpm]
Cor
r. To
rque
[Nm
]
0
50
100
150
200
250
Cor
r. P
ower
Pe
[kW
]
after break-inafter 100 hrsafter 179 hrs
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
]
after break-inafter 100 hrsafter 179 hrs
Engine "B": 66411563MMT
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
]
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
Engine Speed n [rpm]
Cor
r. To
rque
[Nm
]
0
50
100
150
200
250
Cor
r. P
ower
Pe
[kW
]
after break-inafter 100 hrsafter 179 hrs
Engine "A": 66411565Super-Plus
Pe
Md
99
MMT- Fuel Additive: WOT-Results
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
Engine "A": 66411565Super-Plus
378371
362
237229
223
150
200
250
300
350
400
after break-in after 100 hrs after 179 hrs
Max
. red
. Dre
hmom
ent [
Nm
]
0
50
100
150
200
250
Max
. Cor
r. P
ower
Pe,
max
[kW
]
Md,max Pe,max
Engine "B": 66411563MMT
5 % Loss of max. Power3 % Loss of max. Torque
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
Engine "A": 66411565Super-Plus
378371
362
237229
223
150
200
250
300
350
400
after break-in after 100 hrs after 179 hrs
Max
. red
. Dre
hmom
ent [
Nm
]
0
50
100
150
200
250
Max
. Cor
r. P
ower
Pe,
max
[kW
]
Md,max Pe,max
Engine "B": 66411563MMT
5 % Loss of max. Power3 % Loss of max. Torque
1010
MMT- Fuel Additive: WOT-Results
304 310 317
0
50
100
150
200
250
300
350
400
after break-in after 100 hrs after 179 hrs
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
after break-in after 100 hrs after 179 hrs
Abg
asge
gend
ruck
p3
bei n
= 6
850
1/m
in [m
bar]
Engine "B": 66411563MMT
6 % Increase of Exhaust Gas Back Pressure at Rated Speed
304 310 317
0
50
100
150
200
250
300
350
400
after break-in after 100 hrs after 179 hrs
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
after break-in after 100 hrs after 179 hrs
Abg
asge
gend
ruck
p3
bei n
= 6
850
1/m
in [m
bar]
Engine "B": 66411563MMT
6 % Increase of Exhaust Gas Back Pressure at Rated Speed
1111
MMT- Fuel Additive: WOT-Results
200
225
250
275
300
325
350
375
400
1000 2000 3000 4000 5000 6000 7000
Engine Speed n [rpm]
Spe
z. K
rafts
toffv
erbr
auch
be
[g/k
Wh]
Engine "B": 66411563MMT
200
225
250
275
300
325
350
375
400
1000 2000 3000 4000 5000 6000 7000
Engine Speed n [rpm]
Spe
c. F
uel C
onsu
mpt
ion
bsfc
[g/
kWh]
after break-inafter 100 hrsafter 179 hrs
Engine "A": 66411565Super-Plus
Brake Spec. Fuel Consumtionup to 5 % higher
200
225
250
275
300
325
350
375
400
1000 2000 3000 4000 5000 6000 7000
Engine Speed n [rpm]
Spe
z. K
rafts
toffv
erbr
auch
be
[g/k
Wh]
Engine "B": 66411563MMT
200
225
250
275
300
325
350
375
400
1000 2000 3000 4000 5000 6000 7000
Engine Speed n [rpm]
Spe
c. F
uel C
onsu
mpt
ion
bsfc
[g/
kWh]
after break-inafter 100 hrsafter 179 hrs
Engine "A": 66411565Super-Plus
200
225
250
275
300
325
350
375
400
1000 2000 3000 4000 5000 6000 7000
Engine Speed n [rpm]
Spe
z. K
rafts
toffv
erbr
auch
be
[g/k
Wh]
Engine "B": 66411563MMT
200
225
250
275
300
325
350
375
400
1000 2000 3000 4000 5000 6000 7000
Engine Speed n [rpm]
Spe
z. K
rafts
toffv
erbr
auch
be
[g/k
Wh]
Engine "B": 66411563MMT
200
225
250
275
300
325
350
375
400
1000 2000 3000 4000 5000 6000 7000
Engine Speed n [rpm]
Spe
c. F
uel C
onsu
mpt
ion
bsfc
[g/
kWh]
after break-inafter 100 hrsafter 179 hrs
Engine "A": 66411565Super-Plus
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
2020MMT- Fuel Additive:
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
2121MMT- Fuel Additive:
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.