Alternate FuelsA View into Gasoline

Tom Weyenberg

Outline

• What is gasoline?

• Ethanol blended gasoline

• The role of additives

• Gasoline performance measurements

Point #1:  Not All Gasoline is the Same!

• 140 billion gallons/year in the US– ~138 refineries in 48 states– Plus bulk gasoline imports

• Refined from a variety of crude oils– US, Canada, Caribbean, Middle East– Light/Heavy/Sweet/Sour

• Using a variety of refinery processes– Crude distillation– Alkylation– Reformation– Cracking

• Gasoline is blended with oxygenates, mainly ethanol

Crude Oil Production

• Extracted from reservoir

• Separation of gases and production water

Crude Oil Transport

• Moved by pipeline and/or ship to a refinery

Refining

• Processed into various products

• Moved to fuel terminal (usually by pipeline)

Fuel Terminal

• Used for storage before use

• Moved by tanker to filling station tanks

Filling Station

• Moved into the vehicle fuel tank

From Well to WheelsQuality is Built In Throughout the Chain

At the Refinery ‐ Crude to Gasoline

Crude Oil(42 Gallon Barrel)

Products made from a barrel of crude

Gasoline 46%

Diesel and Home Heating26%

Other Products 12%

Jet Fuel 9%

Liquified Petroleum 4%Asphalt 3%

Source: EIA

Lt. ends plantGas and

light gasoline

Liquefied petroleum

gas Butanes

Light straight run gasoline

Isomerization plant Isomerate

ReformateReformer

Alkylation plant

Alkylate

Gasoline

Naphtha

Kerosene

DieselAtm

osph

eric

dis

tilla

tion

Crude oil

AGO

VGOVacuum Distillation

Residuum

Catalytic cracker

Hydro-cracker

HCO

Coker

Light Cycle Oil

Fuel oil

Hydro-treater

Jet

Diesel

CokeAsphalt

Pathways to Gasoline

At the Terminal – Blending Ethanol• Ethanol is too corrosive to ship by pipeline, so it is blended

into gasoline at the terminal

• Refineries make gasoline to a specification (BOB) such that addition of fuel grade ethanol at a terminal brings the final gasoline into specification

• Deposit Control Additives are also added at the terminal

Most gasoline in the US is now blended with 10% ethanol

Gasoline

Ethanol

1.2% 0.8% 1.0% 1.1% 1.1% 1.3% 1.3% 1.5%2.1%

2.5% 2.9%

3.9%

4.8%

7.0%

8.0%

9.3% 9.6%

0%

2%

4%

6%

8%

10%

12%

0

500,000

1,000,000

1,500,000

2,000,000

2,500,000

3,000,000

3,500,000

4,000,000

1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011

Etha

nol B

lend

 (%)

Prod

uctio

n (Tho

usan

ds of B

arrels)

U.S. Gasoline and Ethanol Production

Source: EIA

At the Pump – Consumer Choices• Brand – part of what

drives consumer choice

• Octane level• Regular / Mid /

Premium• OEM requirement

and consumer perception

• Behind the scenes• Quality control• Tank hygiene• Fuel supplier /

f

Most filling stations receive gasoline from a nearby terminal located on a product pipeline. Marketers pulling from a terminal get the same basic gasoline, although 

additive type and level may be different.

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

2010

2011

U.S. Market Share (by product grade)

Regular Midgrade Premium

Source: EIA

Point #2:  Gasoline quality is Highly Regulated

• Complex patchwork of federal, state and industry specifications:– ASTM D4814‐12– California CaRFG Phase 3– EPA Tier 2 fuel regulations (Tier 3 proposed)– Federal RFS drives ethanol usage, as well as state and local factors, including subsidies and mandates

– Octane limits set and regulated at state level

Basic Gasoline Specifications• Composition

– Max sulfur – Max benzene– Max aromatics– Max olefins– Limits on other elements (lead, manganese, phosphorous)

• Physical properties– Vapor pressure, RVP (varies by season and geography)– Distillation and final boiling point– Oxygen content (typically from ethanol)– Oxidative stability

Point #3:   Ethanol blended gasoline is here to stay, the question is how high does the E level go?

Point #3A:   Ethanol presents some challenges to gasoline performance.

Ethanol• Ethanol is a renewable fuel made from high energy density 

plant sources such as corn and sugar cane– Ethanol is a gasoline blending stock (E10 = 10% ethanol blend)

• Fuel ethanol specifications:  ASTM D4806‐1a– Composition

• Ethanol• Methanol max• Denaturant min/max (typically gasoline)• Water max• Gums max• Other elements max (chloride, copper, sulfur)

– Properties• pH• acidity

The Ethanol Controversy• Green movement meets farm lobby, date, then break up.• The case for:

– Renewable– Domestic and good for farm economies– Replacement oxygenate for MTBE

• The case against:– Lifecycle Analysis: not as green as you might think

• LCA Carbon, fertilizer runoff, water use, alternate land use

– Heavily subsidized:  excise tax credits, direct investment, RIN credits – Driving up food prices “food for fuel”– 30% lower BTU energy content – Performance issues:  corrosion, intake valve deposits, hot running, shortened 

engine life  

• The reality:– Approaching 10% ethanol in all gasoline, while E85 remains a niche– At the “blend wall”, yet mandates in Federal RFS to further increase ethanol 

usage

The E15 Ethanol Outlook• EPA has approved E15 for use in MY 

2001 and later vehicles– Exceptions for motorcycle, off road (i.e. 

boat, lawnmower)– Investigating approval for older vehicles

• Lawsuits filed – Numerous organizations testing, showing 

engine and fuel system damage from E15

• Not allowed in California• Marketers are holding off on E15

– Liability for damage from mis‐fueling– Fuel station infrastructure limits– Expense of blender pumps

The E15 controversy is keeping ethanol and its negative effects high in the consumers mind.

Source: US EPA

Ethanol Water Tolerance• If ethanol blended gasoline becomes contaminated with too 

much water, phase separation will occur.– Example:  E10 will phase separate at 0.3% ‐ 0.5% water

• When phase separation occurs, the blend separates into two layers:  gasoline on top, ethanol/water on bottom.

• Phase separation is more likely to occur with:– Higher amounts of water contamination– Lower temperatures

• Standard recommendation when phase separation occurs is to remove separated fuel and clean the fuel tank.

Ethanol and Intake Valve DepositsE0 and E10 IVD Comparison in ASTM D5500 BMW Test

• 4K‐16K km intake valve deposit test length

• Identical base and additized fuels tested with (E10) and without (E0) 10% ethanol

• Over all comparisons, E10 IVD was significantly higher than E0– E10 IVD 41% higher than E0– >95% confidence

• The delta was strongest in the ‘same‐vehicle’ subset– E10 IVD 67% higher than E0– >95% confidence

• Effective additive can overcome the increased fouling propensity

Comparison of E0 and E10 IVD in BMW Tests

0

50

100

150

200

250

300

350

0 100 200 300 400

E0 IVD (mg/valve)

E10

IVD

(mg/

valv

e)

same vehicledifferent vehicles

Ethanol and Intake Valve DepositsHighest deposit concerns around E10‐E15

• The impact of ethanol on intake valve deposits has been shown to exhibit a maximum at or around 10% ethanol (E10). However, even E85 and E100 form IVD

0

50

100

150

200

250

300

350

0 20 40 60 80 100Ethanol Content of Fuel (vol %)

Inta

ke V

alve

Dep

osits

(mg)

No Additive

Desired Deposit Level

Point #4:  Deposit control additives are used in all US fuels, at varying levels

• Deposit Control Additives are used to keep fuel system components clean, which impacts vehicle emissions, fuel economy and performance.

• By law, all gasoline sold in the US must contain deposit control additive at a minimum performance level.  Some fuel marketers use deposit control additives to give higher level performance.

• Additive packages are formulated with other performance components to protect fuel and provide differentiation.

What’s in a typical bulk gasoline additive?

CleanDirty

Impaired Fuel Flow

Better Air/Fuel mixing

Poor Cold Start

Decreased Maintenance

Gasoline Deposit Control Additives

CleanDirty

Poor Fuel Distribution

Better Fuel Atomization

Unburned HydrocarbonsReduced Emissions

Loss of PowerImproved Fuel Economy

Gasoline Deposit Control Additives

Gasoline Fuels and AdditivesThe Main Performance Levels

• LAC – Required by the US EPA everywhere in the US

• CARB – Required in California

• TOP TIER™– Higher performance level recommended by GM, BMW, Honda, Toyota, VW and Audi

• Differentiated ‐ Some marketers use additive levels well above TOP TIER

Gasoline Fuels and AdditivesPerformance Levels

• LAC – Required by the US EPA– Using EPA 65th percentile fuel

• ASTM D5500 BMW Intake Valve Deposit Test– Additized fuel must give <100 mg/valve IVD– Using base fuel that gives > 290 mg/valve

• ASTM D5598 Chrysler Fuel Injector Test – less than 5% flow loss

• CARB – California Only– US EPA LAC plus– Using CARB PIII fuel (tightly specified)

• ASTM D5500 BMW less than 50 mg IVD• ASTM D5500 BMW less than 140% of base fuel Combustion Chamber Deposits (CCD)

CARB uses the same IVD test as US EPA’s LAC requirement, with a stricter deposit limit and a defined base fuel.

Gasoline Fuels and AdditivesPerformance Levels

• TOP TIER – Developed and recommended by GM, Honda, BMW, Toyota and VW– Using fuels specified and severity tested 

• ASTM D6201 Ford Intake Valve Deposit– Additized fuel less than 50 mg/valve– Using Base fuel >500 mg/valve

• ASTM D6201 Ford less than 140% of base fuel CCD

• GM SCPI injector sticking test• GM intake valve sticking no‐harm test

– To claim TOP TIER all octane levels must meet performance specifications

TOP TIER uses four engine/vehicle tests using somewhat more modern engines: 1994 vs. 1985

Point #5:  Higher levels of deposit control additives provide real 

performance benefits to the consumer.

Point #5A:  CARB gasoline is in‐between EPA‐LAC and TOP TIER on 

deposit control performance.

Gasoline Fuels and AdditivesPerformance Levels

• Deposit Prevention Ranking:EPA LAC < CARB < TOP TIER

EPA LAC CARB TOP TIER™

Requirement Required in U.S.

Required in California

Premium differentiated treatment

IVD performance:D5500 (BMW) Base Fuel >290 mg >290 mgD5500 (BMW) Additized <100 mg <50 mgD6201 (Ford 2.3L) Base Fuel

>500 mg

D6201 (Ford 2.3L) Additized

<50 mg

Additive Treat Rate,expressed as multiple of EPA LAC level

1X 1.5‐2.0X 2.5‐3.0X

Deposit Control ComparisonASTM D6201, Ford 2.3L IVD test

• Fuels sampled from filling stations: Unleaded regular, 87 Octane• Run in industry standard engine test, ASTM D6201• 4th quarter 2012

LAC Gas TOP TIER Gas Differentiated Gas

731 mg 97 mg 9.8 mg

CARB Gasoline Average PropertiesGRADE AVERAGE

90% EVAP

AVERAGECORRECTEDAROMATICS

AVERAGECORRECTEDOLEFINS

AVERAGESULFUR(D5453)

Deg. F Vol % Vol % ppm wt.

National 316.8 25.0 6.8 24.8

CARB 308.3 22.7 3.7 5.8

128

• CARB gasoline on average has lower aromatics, olefins and sulfur when compared to other states.

• Combined with deposit control additive requirements under CARB protocol, on average CARB fuel is better than the national average gasoline treated at LAC level.

• However, CARB gasoline is not at the TOP TIER level, both in comparing specifications and as proven in testing.

California Market Fuels Test ResultsASTM D6201 Ford Intake Valve Deposit Test 

Location Brand Grade Test Lab

Avg. IVD Weight

Result (mg)

TOP TIERIVD

Pass/Fail

Limit<50 mg

Culver City CA A Regular SWRI 22.2 Pass

El Monte CA B Regular SWRI 88.6 Fail

Venice CA C Regular SWRI 36.2 Pass

Concord CA A Regular Lubrizol 32.4 Pass

San Bernardino CA A Regular Lubrizol 116.8 Fail

129

40% of CARB gasoline samples run in an industry standard engine test did not meet TOP TIER IVD requirements

Summary• Not all gasoline is the same• Gasoline quality is highly regulated• Ethanol blended gasoline is here to stay.  The question is how high does the E level go?

• Ethanol causes fuel system issues, some of which can be corrected with additives

• Deposit control additives are used in all US fuels, at varying levels

• Deposit control:  EPA‐LAC < CARB < TOP TIER < Differentiated

• CARB gasoline does make deposits

Contact: Tom WeyenbergThe Lubrizol Corporationtom.weyenberg@lubrizol.com440-347-1301