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APBFAPBF--DEC Lubricants ProjectDEC Lubricants Project

Presented by:

Shawn D. Whitacre, NREL

Presented at:

4th JCAP ConferenceTokyo, Japan

June 1, 2005

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APBF-DEC Participants

AutomobileAutomobile• Ford• GM• DaimlerChrysler• Toyota

GovernmentGovernment• DOE• NREL• ORNL• EPA• CARB• SCAQMD

TechnologyTechnology

• Battelle

EnginesEngines• EMA• Caterpillar• Detroit Diesel• Cummins• John Deere• Mack Trucks• International

Truck & Engine

Emission ControlEmission Control

• MECA • Johnson Matthey• Delphi • 3M • Engelhard

• Siemens • Benteler • ArvinMeritor • Clean Diesel Tech. • Corning

• Donaldson Co. • OMG• NGK • Rhodia • Argillon

• Tenneco Automotive • Robert Bosch

Energy/AdditivesEnergy/Additives

• API • American Chemistry Council• BP • Castrol • ChevronOronite

• Chevron • Ciba • Ergon • Afton • ExxonMobil • Infineum

• Lubrizol • Marathon Ashland • Motiva • NPRA

• Pennzoil-Quaker State • Shell Global Solutions • Valvoline

• ConocoPhillips • Crompton

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Two-Phase Approach

Engine-out Catalyst-out

OilOil

Phase IPhase I Phase IIPhase II

EmissionControlDevice

EmissionControlDevice

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Objectives

• Part 1: Characterize effects of lubricant properties on engine out emissions

• Part 2: Develop methods to accelerate exposures of emission control systems (ECS) to lubricant-derived emissions

Phase IPhase I

Determine the impact of lubricant properties and composition on engine-out/catalyst-in emissions

Determine if lubricant formulation impacts the performance and durability of diesel engine ECS

Phase IIPhase II

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Desired OutcomeDetermine which (if any) lube derived emission components are detrimental to ECS performance and durability

• Engine manufacturers

• ECS suppliers

Guidelines for lubricant formulation

Guidelines for lubricant formulation

• Basestock selection

• Additive chemistry

Design guidelinesDesign guidelines

The results will provide:

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Phase 1

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Phase 1Base Oils

• Group I: Valero (Paulsboro)• 4800-5600-ppm S, 75% saturates

• Group II: Excel (Lake Charles)• <20-ppm S, >99% saturates

• Group III: Motiva (Port Arthur, TX)• <5-ppm S, >99% saturates

• Group IV: BP• PAO (poly-alpha olefin, synthetic)• 0 sulfur• 5% ester for additive solubility (from Uniqema)

Phase I - Part 1Phase I - Part 1

Lubricant SelectionLubricant Selection

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8

Ash 0 – 1.85%Sulfur 0 – 6590-ppmCalcium 0 – 4770-ppmZinc 0 – 1900-ppmPhosphorus 0 – 1700-ppmMagnesium 0 – 1700-ppmBoron 0 – 1235-ppm

Phase I - Part 1Phase I - Part 1

Additive PackagesLubricant SelectionLubricant Selection

• Five suppliers (Ciba, Chevron, Ethyl, Infineum, and Lubrizol) provided specifications on 26 candidate additive packages

• Five suppliers (Ciba, Chevron, Ethyl, Infineum, and Lubrizol) provided specifications on 26 candidate additive packages

• Range of constituents (in Group II base oil)• Range of constituents (in Group II base oil)

• Supplier and source of constituents not specified• Supplier and source of constituents not specified

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Test Laboratory – Phase I

• Subcontractor: Automotive Testing Laboratories, (East Liberty, OH)

• Subcontractor: Automotive Testing Laboratories, (East Liberty, OH)

Phase I - Part 1Phase I - Part 1

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Test Engine

• 7.3L OHV V-8• Direct injection, turbocharged w/ wastegate• HEUI fuel system• 215 hp at 2400 rpm• 540 ft-lbs torque at 1500 rpm• Exhaust gas recirculation (retrofit)• Closed crankcase ventilation with filter• Lube system capacity: 18 quarts

Phase I - Part 1Phase I - Part 1

• 1999 International T444E• 1999 International T444E

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12

3

4

Test Modes and Emissions Measurements

Four Mode Steady-State (OICA)• Mode 1: Rated Condition• Mode 2: High Torque• Mode 3: Road Load• Mode 4: Low Torque

Emissions Measurements• Gases (HC, CO, CO2, NOx, SO2)• PM – three sampling trains

– TPM, SOF, SO4

– Metals– PAHs

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3

4

800

700

600

500

400

300

200

100

0700 1200 1700 2200 2700

Speed (RPM)To

rque

(N

m)

Phase I - Part 1Phase I - Part 1

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Data Analysis Questions #1 and #2

• Are there significant differences in engine-out emissions that can be attributed to oil properties?

• If so, how much of an impact is due to properties of the additive package? …base oil?

Phase I - Part 1Phase I - Part 1

1

2

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SO2 Emissions – Significant Additive and Base Oil Effects• Additive packages

c and i produced highest SO2emissions

• Significant base oil effect – Group 1 highest

• Magnitude of the effects do not directly correlate with sulfur content of oil

4-Mode OICA Weighted0.018

0.000

0.002

0.004

0.006

0.008

0.010

I II III IV I II III IV I II III IV I II III IV I II III IV I II III IV II II II II II II II II

a b c d e f g h i j k l r* r**

Base Oil/Additive

Adj

. SO

2 (g

/Bh

p-H

r)

*Pre-aging. **Post-aging.

8930-ppm S(Highest)

8930-ppm S(Highest) 3500-ppm S3500-ppm S

245-ppm S(Lowest)

245-ppm S(Lowest)

Phase I - Part 1Phase I - Part 1

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Also… Significant Effects of Additive Packages and Base Oils on SO2

• Many significant differences among the 6 additive packages tested in all four base oils

• Significant base oil effect – Group 1 highest

• No significant interactions between additive packages and base oils

Phase I - Part 1Phase I - Part 1

4-Mode OICA Weighted

0.000

0.001

0.002

0.003

0.004

0.005

0.006

A Z Y M B T 1 3 2 4

Effect of Additive Package Effect of Base Oil

Adj

. SO

2 (g

/Bhp

-Hr)

Main Effects of Additives and Base Oils

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Data Analysis Question #3

Which emissions species can be directly predicted from the properties of the oil and fuel?

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Phase I - Part 1Phase I - Part 1

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Mass Balance

• Metals • SO4• Metals • SO4

• SO2• SO2

• Emissions from fuel and oil consumptions and wear metals

• Recovery rates obtained by comparing measured emissions with calculated values based on fuel and oil properties

Phase I - Part 1Phase I - Part 1

FuelFuel

Lube OilLube Oil

PMEmissions

PMEmissions

GaseousEmissionsGaseous

Emissions

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Ca Mass Balance• Ca emissions directly

correlated with concentration in oil

• No apparent composition effects

• 42% recovery rate

• Ca emissions directly correlated with concentration in oil

• No apparent composition effects

• 42% recovery rate

0.0

0.2

0.4

0.6

0.8

1.0

0.0 0.2 0.4 0.6 0.8 1.0

x=y

Mea

sure

d Va

lue

(mg/

Bhp

-Hr)

Calculated Value (mg/Bhp-Hr)

Phase I - Part 1Phase I - Part 1

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P Mass Balance

0.0

0.1

0.2

0.3

0.4

0.5

0.0 0.1 0.2 0.3 0.4 0.5

Calculated Value (mg/Bhp-Hr)

Mea

sure

d Va

lue

(mg/

Bhp

-Hr)

x=y

• P emissions directly correlated with concentration in oil

• Oil c2, c3 and c4 deviate significantly

• 86% recovery rate (excl. Oils c2, c3 and c4)

• P emissions directly correlated with concentration in oil

• Oil c2, c3 and c4 deviate significantly

• 86% recovery rate (excl. Oils c2, c3 and c4)

Phase I - Part 1Phase I - Part 1

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Sulfur Mass Balance (continued)

• S emissions directly correlated with concentration in oil

• Oil i significantly deviates

• 125% recovery rate (excl. Oils i)

• S emissions directly correlated with concentration in oil

• Oil i significantly deviates

• 125% recovery rate (excl. Oils i)

8.08.0

9.210.2

0

1

2

3

4

0 1 2 3 4Calculated Value (mg/Bhp-Hr)

Mea

sure

d Va

lue

(mg/

Bhp

-Hr)

Oil a* Oil b* Oil c*

Oil d* Oil e* Oil f*

Oil g* Oil h* Oil i*

Oil j* Oil k* Oil l*

Oil a(I) Oil b(I) Oil c(I)

Oil d(I) Oil e(I) Oil f(I)

Oil a(III) Oil b(III) Oil c(III)

Oil d(III) Oil e(III) Oil f(III)

Oil a(IV) Oil b(IV) Oil c(IV)

Oil d(IV) Oil e(IV) Oil f(IV)

Oil i r*-Pre r-Pre

r*-Post r-Post Pred.

x=y

*Tested using fuel w ith 4.54 ppm sulfur. Note: Oil c1 excluded.

8.08.0

9.210.2

0

1

2

3

4

0 1 2 3 4Calculated Value (mg/Bhp-Hr)

Mea

sure

d Va

lue

(mg/

Bhp

-Hr)

Oil a* Oil b* Oil c*

Oil d* Oil e* Oil f*

Oil g* Oil h* Oil i*

Oil j* Oil k* Oil l*

Oil a(I) Oil b(I) Oil c(I)

Oil d(I) Oil e(I) Oil f(I)

Oil a(III) Oil b(III) Oil c(III)

Oil d(III) Oil e(III) Oil f(III)

Oil a(IV) Oil b(IV) Oil c(IV)

Oil d(IV) Oil e(IV) Oil f(IV)

Oil i r*-Pre r-Pre

r*-Post r-Post Pred.

x=y

*Tested using fuel w ith 4.54 ppm sulfur. Note: Oil c1 excluded.

Phase I - Part 1Phase I - Part 1

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Phase I Conclusions

• Lubricant formulation has modest effects on regulated emissions • +10% for CO and NOx, +20% for PM, and +30% for HC

• Sulfur content in the oil has significant effects on sulfur emissions.

• However, oil formulation (beyond oil sulfur content) can have a significant impact on SO2emissions (e.g. oils c and i)

• Metals (S, P, Zn, Ca) emissions correlate with concentration in oil

Phase I - Part 1Phase I - Part 1

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Phase 2

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Test Laboratory – Phase 2

• Subcontractor: Analytical Engineering, Inc. (AEI) Columbus, Indiana

• Subcontractor: Analytical Engineering, Inc. (AEI) Columbus, Indiana

Phase I - Part 1Phase I - Part 1

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Test Hardware – Phase 2

2002 Cummins ISB – 300 hp @ 2500 rpm5.9L, inline 6 cylinderCooled-EGRSingle NOx adsorber (7L)In-pipe regeneration fueling

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Test Protocol

400-hour testEvaluations at 100-hour intervals

- Focus on NOx reduction efficiencyOil consumption measurementNew LNT for each testOil change at 200-hoursDEC base fuel (0.6-ppm S/15-ppm S)Post-analysis of catalyst by XRF

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Operating Modes

Mode

Engine Speed (RPM)

Load (FT*Lbs)

Average Catalyst

Mid Temp. ºF

(ºC)

Space Velocity (1/hr)

1 1650 140 650 (343) 30,000 2 2100 175 650 (343) 70,000 3 1400 160 750 (399) 32,000 4 1900 225 750 (399) 63,000 5 1200 275 850 (454) 33,000 6 1700 350 850 (454) 62,000

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Phase 2 Analysis Approach

Engine-outEmissions

TailpipeEmissions

OilOilNOx

AdsorberCatalyst

NOxAdsorberCatalyst

Fuel/OilProperties

CatalystDeposits

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Test Matrix

ZDDP Level

Calc

ium

Det

erge

nt L

evel

A

DEF

B

C

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Properties of Test Oils

Viscosity

Test Number

Ash* (%)

S* (ppm)

Ca (ppm)

P (ppm)

Zn (ppm)

N* (ppm)

TBN (mg

KOH/g)@100ºC

(cSt)

@40ºC

(cSt) Soot (%)

1 0.775 1695 1853 427 471 1128 6.99 14.9 111.3 0.07 2 1.522 2928 3258 1210 1320 1329 12.34 15.0 111.9 0.06 3 1.131 3980 2050 1430 1590 1477 7.3 15.0 111.9 0.06 4 1.316 4195 3160 1340 1520 1314 10.6 15.0 112.5 0.12 5 1.310 2228 3241 419 475 1368 9.6 14.6 107.7 0.12 6 1.497 4197 3518 1280 1480 1315 10.2 14.7 109.1 0.11 7 0.775 1695 2065 451 505 1128 6.7 14.9 110.9 0.08 8 0.775 1695 2329 483 546 1128 8.7 14.9 110.9 0.11

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Catalyst Deposit Profile

Sulfur

0%

20%

40%

60%

80%

100%

Front Middle Rear

Catalyst Position

Per

cent

of T

otal

Su

lfur

Depo

sits

Phosphorus

0%

20%

40%

60%

80%

100%

Front Middle Rear

Catalyst PositionPe

rcen

t of T

otal

Ph

osph

orou

s D

epos

its

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Phosphorus Impact on PerformanceC

hang

e in

NO

x R

educ

tion

Effic

ienc

y (%

)

-80%

-60%

-40%

-20%

0%

0.0 0.1 0.2 0.3 0.4 0.5Phosphorous Exposure over 400 Hours of Aging (g/liter)

A-1 A-7 B-3 E-2 F-4 C-5 D-6Lubricant-Test Number:

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Impact of DetergentA

vera

ge S

ulfu

r + P

hosp

horo

us D

epos

its (g

/lite

r)

0

1

2

3

4

0.5 1.0 1.5 2.0 2.5

Exposure Amount (g/liter)Low Ca Sulfonate High Ca Sulfonate High Ca Phenate High Ca Salicylate

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Relative Impact of Fuel and Lube S

Composite ModeNOx Reduction Efficiency

0

20

40

60

80

100

0 100 200 300 400

Hour

NOx

Redu

ctio

n Ef

ficie

ncy

(%)

Tests A-1 and A-7 with 0.6 ppm Sulfur FuelTest A-8 with 15 ppm Sulfur Fuel

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Preliminary Conclusions – Phase 2Final reporting still in progress

Will be available late 2005

Sulfur and phosphorus in lube oil appear to impact LNT performanceDeposits of lube oil derived species concentrated on front of catalystDetergent level may temper the effectFuel sulfur still appears to be dominant in terms of degradation

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THE END