EVALUATION OF E85 FUELS

Presented at the 6 th Annual Fuel Ethanol Laboratory Conference 11-13-13 By Jerry King

THE PROJECT

• • • • • Randomly select five Omaha metro E85 facilities Collect one (1) Liter of E85 into an aluminum container Analyze the samples following ASTM D5798 • • • Report results for • • • • Anions (chloride & sulfate) Ethanol and methanol Washed and unwashed gum Moisture and pHe Specific gravity and vapor pressure Acidity Copper and sulfur Compare results with each other and D5798

E85 PATHWAY

Hydrocarbon Source D 4814 Ethanol Source D 4806 E85 D 5798 shipped blended Additives Distribution Pump Vehicle

THE CHALLENGE(S)

• • • • Produce a quality product • Meet/exceed ASTM D5798 specifications • Producers (ethanol and hydrocarbon) • Automobile industry • Consumers (vehicle operators) Make a profit • Sell directly to the consumer or distributor Comply with Federal and State regulations • Component standards • Operational standards Address the needs of • Service stations • Vehicle owners

ASTM 5798-13a

• • Approved by ASTM D02A June 15, 2013 and published July 2013 Critical components of the standard • To contain 51 – 83 volume % ethanol • Four classes based on vapor pressure - kPa (psi) • Class 1: 38 – 62 kPa or 5.5 – 9.0 psi • Class 2: 48 – 65 kPa or 7.0 – 9.5 psi • • Class 3: 59 – 83 kPa or 8.5 – 12.0 psi Class 4: 66 – 103 kPa or 9.6 – 15.0 psi • Variable vapor pressure requirements to meet seasonal climatic changes • Ethanol content and hydrocarbon blendstock are adjusted by the blender to meet vapor pressure requirements • Agreement between purchaser and seller to denote vapor pressure class at the time and place of bulk delivery

US VOLATILITY SPECIFICATIONS • • TABLE 3 of ASTM D5798 Based on month of the year – example Nebraska • Jan - 4 • • Feb - 4 Mar - 4/3 • April - 3/2 • • May - 2 June - 2/1 • • July - 1 August - 1/2 • Sept - 2 • • Oct - 2/3 Nov - 3/4 • Dec - 4

ETHANOL FUEL BLEND REQUIREMENTS • • • • • • • • • From Table 1 - ALL CLASSES must meet: • Ethanol volume % - 51 – 83 • Water content, max, mass % - 1.0

Methanol content, max, volume % - 0.5

Sulfur content, max, mg/kg - 80 Acidity (as acetic acid) mass % max, - 0.005

Solvent washed gum content, max, mg/100 mL - 5 Unwashed gum content, max, mg/100 mL - 20 pHe - 6.5 – 9.0

Inorganic chloride content, max mg/kg - 1 Copper content, max, mg/L - 0.07

HYDROCARBON BLENDSTOCK REQUIREMENTS • • • • FROM TABLE 2 of ASTM D5798 • Distillation end point, max degrees C - 225 or 437 degrees F • Oxidation stability, min. minutes - 240 Copper strip corrosion, max, - No. 1 Silver strip corrosion, max - No. 1 Vapor pressure - report • Note - vapor pressure is to be known in order to choose a suitable blend ratio for the components to meet vapor pressure requirements of a particular volatility class

WORKMANSHIP REQUIREMENTS • • • • Comply with part 6 of ASTM 5798 • Free of sediment • Clear and bright Free of any adulterant or contaminant Any ethanol or blendstock containing silicon-containing materials To deliver a quality product, the producer (you) must know what goes into the product • Sometimes difficult to test a parameter (no recognized ASTM standard) • Must know how to test the components and maybe the final product • Who holds the responsibility of a defective/non-spec product????

COMPARATIVE DATA FOR FIVE (5) E85 SAMPLES

• Compare results with each other and the standard

1 0 3 2 9 8 5 4 7 6

Vapor Pressure (DVPE)

Vapor Pressure (DVPE) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

VAPOR PRESSURE

• • Samples collected in Omaha in September Table 3 indicates Class 2 in September • • Class 2 7.0 – 9.5 psi All samples in specification, but at the low end of vapor pressure • Product • Carry-over from August which is class 1 or 2 (1 / 2) 5.5 – 9.0 psi for class 1

Grabner Vapor Pressure Instrument (Used for Vapor Pressure - ASTM D5191)

90 80 30 20 10 0 70 60 50 40

Ethanol Percentage (%Vol)

Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798 (upper) ASTM 5798 (lower) Ethanol Percentage (%Vol)

ETHANOL CONTENT

• Looks like two different suppliers • Two locations with about 80% ethanol • Three locations with about 68% ethanol • ALL FIVE WITHIN “SPEC”

Bruker 436 - GC Gas Chromatograph (Used for Ethanol & Methanol - ASTM D5501)

ASTM D5501

• • • GC/FID instrument (flame ionization detector) Standard curve is prepared using increasing concentrations of ethanol Develop a response factor or use theoretical as found in the method

Moisture, Karl Fisher (%Mass)

0,6 0,4 0,2 0 1,2 1 0,8 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798 Moisture, Karl Fisher (%Mass)

AquaStar Coulometric Karl Fischer Instrument (Used for Karl Fischer Moisture - ASTM E1064)

Acidity in Ethanol (%)

0,007 0,006 0,005 0,004 0,003 0,002 0,001 0 Acidity in Ethanol (%) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

Titration Setup for Acidity with Nitrogen Purge (ASTM D7795)

ACIDITY

• • • • Can use ASTM D1613 or ASTM D7795 Both are titration methods – titrate with known base (sodium hydroxide) Results reported as acetic acid Differences in methods • ASTM D1613 – straight titration • ASTM D7795 uses nitrogen blanket • • • Removes the influence/effects of carbon dioxide (CO 2 ) Carbon dioxide from air plus water = carbonic acid (HCO 3 ) Titrated and reported as “acetic acid”

Dionex Ion Chromatograph (used for Chloride & Sulfate - ASTM D7328)

Chloride (mg/kg)

0,6 0,4 0,2 0 1,2 1 0,8 Chloride Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

Sulfate (mg/kg)

1 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0 Sulfate (mg/kg) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

Antek 9000 Series Sulfur Analyzer (Used for Sulfur – ASTM 5453)

90 80 30 20 10 0 70 60 50 40

Sulfur (total) (ppm)

Sulfur (total)(ppm) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

Thermo Scientific Atomic Absorption (AA) Spectrometer (Used for Copper - ASTM D1688)

Copper (mg/kg)

0,1 0,09 0,08 0,07 0,06 0,05 0,04 0,03 0,02 0,01 0 Copper (mg/kg) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

Thermo Scientific Orion 3 Star Bench-Top pH Meter (Used for pHe - ASTM D6423)

10 9 8 1 0 3 2 5 4 7 6

pHe

pHe Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798 (upper) ASTM 5799 (lower)

Anton Parr Digital Densitometer

Specific Gravity (g/mL at 60F)

0,9 0,8 0,3 0,2 0,1 0 0,7 0,6 0,5 0,4 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798 Specific Gravity (g/mL at 60F)

20 15 10 5 0

Gum Residue, Unwashed (mg/100mL)

25 Gum Residue, Unwashed (mg/100mL) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

5 4 1 0 3 2 6

Gum Residue, Washed (mg/100mL)

Gum Residue, Washed (mg/100mL) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

Moisture, Karl Fisher (%Vol)

0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0 Moisture, Karl Fisher (%Vol) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6

Methanol (%Vol)

0,3 0,2 0,1 0 0,6 0,5 0,4 Methanol (%Vol) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ASTM 5798

CONCLUSION(S)

• • • With the exception of copper in one sample, all parameters were “in spec” Sample results showed variability which is to be expected Assume the ethanol plant laboratory obtained about the same results as MWL