An Introduction to Synthetic Base Stocks - AEAaea.org.br/apresentacoes/lub08/Sandra_Mazzo_Skalski.pdf · An Introduction to Synthetic Base Stocks. Sandra Mazzo-Skalski. ExxonMobil

SIMPÓSIO DE LUBRIFICANTES E ADITIVOS28 e 29 de Outubro de 2008

Symposium on Lubricants and

Additives (Brazil, São Paulo 2008)

An Introduction to Synthetic Base Stocks

Sandra Mazzo-SkalskiExxonMobil ChemicalOctober 28, 2008


Objectives• Synthetic Basestocks

– Group IV - PolyAlphaOlefins (PAO)

– Group V - Alkylated Naphthalene and Esters

• Trends in

– Automotive Engine Oils

– Automotive Transmission and Gear Oils

– Industrial Oils

• Bio Fuels – Effect on Lubricants


PAOs are high-performance, tailored fluids made by chemically reacting materials of specific chemical composition to produce compounds with planned and predictable properties.

What are PolyAlphaOlefins (PAO)?

305 10 20 25GC Retention Time (minutes)

PAO 4 cSt

Mineral Oil 4 cSt

15

• Well-defined structure vs. multiple component composition of mineral oil

• Hydrogenated (saturated) olefin polymers

• Manufactured by the catalytic oligomerization of linear alphaolefins

• Wax-free combination of molecules of predetermined chain length


What is an Ester?• Synthesized from organic acids and alcohols to produce

predetermined molecular structures.

• Primarily a polar hydrocarbon which:

– Is thermally and oxidatively stable

– Has a high viscosity index

– Lacks undesirable and unstable impurities found in conventional petroleum based oils

• Structurally differentiated from PAO due to the presence of multiple ester linkages (COOR)

The polar nature of esters drives their performance features.The polar nature of esters drives their performance features.


Polyol Esters

C CH2H2C

CH3

CH2

O

O

C

C

OR

O

R

O

O

R

CH2CH2C

H2C

CH2

O

O

O

O

C

C

C

C

O R

O

R

OR

O

R

Performance Features

Step-out performance capabilities vs

Diesters & Aromatic esters:

– higher thermal stabilities may extend the operating range of lubricant by as much as 50 -100oC

– high film strength and increased lubricity may yield reduced energy consumption in many applications

Performance Features

Step-out performance capabilities vs

Diesters & Aromatic esters:

– higher thermal stabilities may extend the operating range of lubricant by as much as 50 -100oC

– high film strength and increased lubricity may yield reduced energy consumption in many applications

Chemistry

TMP C8/C10

PE Ester

Product Type

Polyol Esters

PE Ester

TMP Ester


Aromatic Esters

DiisohexylDiisononylDitridecylTriisooctylTriisononyl

Trimellitate

Aromatic Esters

Chemistry Product Type

Phthalate

O

O

O

HOR

2+

O

O

O

OR

R

Application Opportunities

Phthalates are used extensively in reciprocating air compressor oils where:

– low viscosity index is the norm

– low cost clean operation is desirable

Trimellitates are often used instead of phthalates if a higher base oil viscosity is needed for improved lubricity:

– often blended with phthalates for higher VG oils

Application Opportunities

Phthalates are used extensively in reciprocating air compressor oils where:

– low viscosity index is the norm

– low cost clean operation is desirable

Trimellitates are often used instead of phthalates if a higher base oil viscosity is needed for improved lubricity:

– often blended with phthalates for higher VG oils

O

O

O

HOR

O

O

O

OR

R3+

O

ORHO

O

Phthalate Trimellitate


• Alkylated aromatic fluids

• Reaction of olefins with naphthalene

• American Petroleum Institute (API) Group V fluids• Synthetic Blendstocks for Automotive and Industrial

Lubricants

What are Alkylated Naphthalenes (AN)?What are Alkylated Naphthalenes (AN)?

Olefins

+ R CH CH2

R

CH3

Catalyst

NaphthaleneCH


5 cSt AN 12 cSt ANSpecific Gravity @15.6/15.6°C 0.908 0.887Viscosity @ 100°C, cSt 4.7 12.4Viscosity @ 40°C, cSt 29 109Viscosity Index 74 105Flash Point, Open Cup, °C 222 258Pour Point, °C -39 -36Noack Volatility, wt% loss 12.7 4.5Total Acid Number (TAN), mg KOH/g < 0.05 < 0.05

Hydrolytic Stability, TAN increase, mg KOH/g 0.02 0.02Oxidation and Corrosion 175°C, 72 hrs TAN increase, mg KOH/g 0.092 0.089RPVOT @150°C without Antioxidant, minutes 196 180RPVOT @150°C with Antioxidant, minutes >1400 >1400Aniline Point, °C 32 90

Alkylated Naphthalene CharacteristicsAlkylated Naphthalene Characteristics


Automotive Engine Oil Trends

Lower oil volumesHigher power densitiesReduced airflow/coolingLonger drain intervalsImproved fuel economy Lower engine emissions

Increased thermal stressBetter oxidation stability

Improved low temperature propertiesLower viscosity gradesImproved wear protection

Lower volatility basestocks

SyntheticSyntheticLubricantsLubricants


Key Areas for Synthetic Fluids in Passenger Vehicle Lubricants

Trend Results in: Recommended Synthetic Basestock

Higher power outputs in more compact engines with lower oil volumes in circulation

Problems with reduced oil life, increased oil consumption

PAOAlkylated Naphthalene

Longer oil drain intervals

Problems with increased viscosity, increased deposit formation, volatility

PAOAlkylated NaphthaleneEsters

Emission legislation and increasing demand for fuel economy

Need for lower volatility and lower viscosity oil, and problems with increased wear


Synthetic basestocks can mitigate the challenges facing modern engine oilsSynthetic basestocks can mitigate the challenges facing modern engine oils


Passenger Vehicle Engine Oil - Key Performance Criteria for Synthetics

Polyalphaolefin (PAO)• Low temperature fluidity & high temperature

viscosity retention• Low volatility• Thermal & oxidative stabilityEsters • Additive solubility• Improved seal compatibility -- balance the

shrinking effect of PAOs

Alkylated Naphthalene (AN)• Additive solubility• Improved seal compatibility -- balance the shrinking effect of PAO’s• Increased additive effectiveness with AN

– AN is less polar versus ester, therefore will not compete with additive for metal surface


PolyAlphaOlefins (PAO) Lower Volatility

PAOs have lower volatility than mineral oils; Low volatility may reduce oil consumption and emissions

PAOs have lower volatility than mineral oils; Low volatility may reduce oil consumption and emissions

0

5

10

15

20

25

30

2 4 6 8 10 12 14Viscosity @ 100 °C, cSt

Noa

ck V

olat

ility

, wt%

Typical Group I and II

Typical Group III

PAO

Mineral Oils


AN Oxidation Resistance in SAE 5W-30 Engine OilsAN Oxidation Resistance in SAE 5W-30 Engine OilsSequence III Screener* Results on SAE 5W-30 GF-4 Engine Oils

Hours

Perc

ent V

isco

sity

Incr

ease

AN improves oxidation stability in market-general GF-4 engine oils formulated with Group II basestocks *ExxonMobil oxidation screening test

AN improves oxidation stability in market-general GF-4 engine oils formulated with Group II basestocks*ExxonMobil oxidation screening test

-50%

0%

50%

100%

150%

200%

250%

300%

0 50 100 150 200 250

Add. Pkg #1 Reference

Add. Pkg. #1 with 10% AN

Add. Pkg. #2 Reference

Add. Pkg. #2 with 10%AN


Alkylated Naphthalene – Polarity Effects on Lubricant Additives

Alkylated Naphthalene can improve additive effectiveness through less competition for the surface.

Alkylated Naphthalene can improve additive effectiveness can improve additive effectiveness through less competition for the surface.through less competition for the surface.

E A A A A AA AE E

Base Oil+Ester +AdditiveE A

Base oil+AN+AdditiveAAN

= Ester Molecule = Additive MoleculeE A AN = AN Molecule


020406080

100120140160

PAO/Ester PAO/AN

Sequence IIIG Wear Performance

of Experimental Low Phosphorus 0W- 30 Engine Oils

Synthetic engine oils blended with PAO and Alkylated Naphthalene demonstrate improved wear performance to PAO/ester formulations. Synthetic engine oils blended with PAO and Alkylated Naphthalene demonstrate improved wear performance to PAO/ester formulations.

Alkylated Naphthalene Improved Antiwear Additive ResponseAlkylated Naphthalene Improved Antiwear Additive Response

Cam

+ L

ifter

Wea

r, um


Automotive Drive Train Fluid Trends

Lower oil volumesHigher power densitiesLonger drain intervalsReduced airflow/coolingImproved fuel economy Improved shiftabilityImproved seal compatibility

Increased thermal stressBetter oxidation stabilityIncreased mechanical stressImproved shear stability

Basestocks with optimised polarity


Improved low temperature propertiesLower viscosity gradesImproved wear protection



Higher power outputs, more compact designs with lower oil volumes in circulation

Problems with higher temperatures and reduced oil life, increased oil consumption


Increasing use of group II & III base oils

Problems with reduced additive solubility, deposit formationLow temperature properties compromised


Increasing demand for fuel economy

Need for Lower volatility oils, Lower viscosities, and problems with increased wear


Key Areas for Synthetic Fluids in Automotive Drive train Fluids

Synthetic basestocks can mitigate the challenges facing automotive drive train fluids

Synthetic basestocks can mitigate the challenges facing automotive drive train fluids


Industrial Oil Trends

Lower oil volumesLonger drain intervalsMore severe operating

conditionsImproved energy efficiency

Increased thermal stressBetter oxidation stabilityIncreased mechanical stressImproved shear stabilityBetter cold start capability


Lower viscosity gradesImproved wear protectionLower traction oils



Higher power outputs, compact designs with lower oil volumes in circulation

Problems with higher temperatures and reduced oil life


Increasing use of group II & III base oils

Problems with reduced additive solubility, deposit formation andLow temperature properties compromised


Increased oil drain intervals

Increasing demands on thermal and oxidation stability of oil


Extended maintenance intervals

Problems with increased wear


Key Areas for Synthetic Fluids in Industrial Lubricants

Synthetic basestocks can mitigate the challenges facing Industrial LubricantsSynthetic basestocks can mitigate the challenges facing Industrial Lubricants


Turbine Oil Stability Test (TOST) ASTM D 943

Alkylated Naphthalene improves oxidative and hydrolytic stability of compressor oils.

Alkylated Naphthalene improves oxidative and hydrolytic Alkylated Naphthalene improves oxidative and hydrolytic stability of compressor oils.stability of compressor oils.

ISO VG 46Compressor Oil

0.0

0.4

0.8

1.2

1.6

2.0

0 500 1000 1500 2000 2500 3000 3500

Time, hr

Total Acid Number, mg KOH/g

PAO / Polyol Ester / Additive

PAO / 5 cSt AN / Additive

Limit

Alkylated Naphthalene in Compressor Oil Formulation


• Oxidative stability of PAO exceeds mineral oil

• Good oxidative stability for applications at elevated temperatures with air contact

• PAOs show excellent oxidative stability when formulated with suitable antioxidants

• PAOs are more responsive to antioxidants than mineral oil.......also to antiwear and other performance additives

PolyAlphaOlefins (PAO) Oxidative Stability

Oxidation Stability TestPAO Vs. Mineral Oil (2% Antioxidant)

Test Conditions: 163oC (325oF), 72 hours

Product

% Vis Change @ 100°CTAN change, mgLead loss, mgSludge

Mineral OilGroup II

215.714.5

160.7moderate

100 cStPAO

1.81.10.2

trace

6 cStPAO

3.50.10.9nil

40 cStPAO

2.60.080.1nil


0

50

100

150

200

250

0% 20% 40% 60% 80% 100%Synesstic™ 5 in Group II Basestock

Tim

e (m

in)

Alkylated Naphthalene - Synergistic Blends with Group II BasestockAlkylated Naphthalene - Synergistic Blends with Group II Basestock

Rotary Pressure Vessel Oxidation Test (RPVOT)

Alkylated Napthalene shows a synergistic effect, yielding improved Group II oxidation performance.

Alkylated Napthalene shows a synergistic effect, yielding improved Group II oxidation performance.


Alkylated Naphthalene - Hydrolytic StabilityAlkylated Naphthalene - Hydrolytic Stability

Replacing adipate ester with AN improves hydrolytic stability in a formulated oil.

Replacing adipate ester with AN improves hydrolytic stability inReplacing adipate ester with AN improves hydrolytic stability in a a formulated oil. formulated oil.

ISO VG 32 Ester blend AN Blend

6 cSt PAO 73 % 73 %

Adipate Ester 25 % ---5 cSt Alkylated Naphthalene --- 25 %

Additives 2 % 2 %

ASTM D 2619

Copper Corrosion, mg/cm² 0.15 0.00

TAN Change, mg KOH/g 0.22 0.03

Total Acidity of Water, mg KOH 19.9 4.9


Bio Fuels – How Will They Effect Lubricants?*

• Biofuels in Brazil– Brazil produces 4.7 billions gallons of

biofuel per year; could double by 2015– More than 40% of transportation fuels

in Brazil are from renewable sources• Ethanol

– Ethanol is a clean-burning, high-octane fuel that is produced from renewable sources.

• produced from sugar cane or corn– Ethanol attracts moisture; lubes need to

have good emulsibility and rust protection

• Biodiesel– Typically, biodiesel fuel is a methyl

ester based on a natural fat or plant oil such as Rapeseed, (RME) Soy (SME), Palm Oil (PME).

– Primary lubricant concern is excess fuel dilution, leading to increased corrosion, oxidation, deposits and wear

*Compiled from Industry resources


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An Introduction to Synthetic Base Stocks - AEAaea.org.br/apresentacoes/lub08/Sandra_Mazzo_Skalski.pdf · An Introduction to Synthetic Base Stocks. Sandra Mazzo-Skalski. ExxonMobil