Fuel ethanol laboratory conference dr. jerry king

Report
EVALUATION OF E85
FUELS
Presented at the 6th Annual Fuel Ethanol Laboratory Conference
11-13-13
By
Jerry King
THE PROJECT
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•
•
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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
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•
•
•
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•
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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
E85
D 5798
Ethanol Source
D 4806
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
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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:
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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
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•
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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
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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
Vapor Pressure (DVPE)
9
8
7
Sample 1
6
Sample 2
5
Sample 3
4
Sample 4
3
Sample 5
2
ASTM 5798
1
0
Vapor Pressure (DVPE)
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)
Ethanol Percentage (%Vol)
90
80
70
Sample 1
60
Sample 2
50
Sample 3
40
Sample 4
Sample 5
30
ASTM 5798 (upper)
20
ASTM 5798 (lower)
10
0
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)
1.2
1
Sample 1
0.8
Sample 2
Sample 3
0.6
Sample 4
0.4
Sample 5
ASTM 5798
0.2
0
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
Sample 1
0.004
Sample 2
Sample 3
0.003
Sample 4
Sample 5
0.002
ASTM 5798
0.001
0
Acidity in Ethanol (%)
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 (CO2)
• Carbon dioxide from air plus water = carbonic acid (HCO3-)
• Titrated and reported as “acetic acid”
Dionex Ion Chromatograph
(used for Chloride & Sulfate - ASTM D7328)
Chloride (mg/kg)
1.2
1
Sample 1
0.8
Sample 2
Sample 3
0.6
Sample 4
0.4
Sample 5
ASTM 5798
0.2
0
Chloride
Sulfate (mg/kg)
1
0.9
0.8
0.7
Sample 1
0.6
Sample 2
0.5
Sample 3
0.4
Sample 4
0.3
Sample 5
0.2
ASTM 5798
0.1
0
Sulfate (mg/kg)
Antek 9000 Series Sulfur Analyzer
(Used for Sulfur – ASTM 5453)
Sulfur (total) (ppm)
90
80
70
Sample 1
60
Sample 2
50
Sample 3
40
Sample 4
30
Sample 5
20
ASTM 5798
10
0
Sulfur (total)(ppm)
Thermo Scientific Atomic
Absorption (AA) Spectrometer
(Used for Copper - ASTM D1688)
Copper (mg/kg)
0.1
0.09
0.08
0.07
Sample 1
0.06
Sample 2
0.05
Sample 3
0.04
Sample 4
0.03
Sample 5
0.02
ASTM 5798
0.01
0
Copper (mg/kg)
Thermo Scientific Orion 3 Star
Bench-Top pH Meter
(Used for pHe - ASTM D6423)
pHe
10
9
8
Sample 1
7
Sample 2
6
Sample 3
5
Sample 4
4
Sample 5
3
ASTM 5798 (upper)
2
ASTM 5799 (lower)
1
0
pHe
Anton Parr Digital Densitometer
Specific Gravity (g/mL at 60F)
0.9
0.8
0.7
Sample 1
0.6
Sample 2
0.5
Sample 3
0.4
Sample 4
0.3
Sample 5
0.2
ASTM 5798
0.1
0
Specific Gravity (g/mL at 60F)
Gum Residue, Unwashed
(mg/100mL)
25
20
Sample 1
15
Sample 2
Sample 3
Sample 4
10
Sample 5
ASTM 5798
5
0
Gum Residue, Unwashed (mg/100mL)
Gum Residue, Washed
(mg/100mL)
6
5
Sample 1
4
Sample 2
Sample 3
3
Sample 4
2
Sample 5
ASTM 5798
1
0
Gum Residue, Washed (mg/100mL)
Moisture, Karl Fisher (%Vol)
0.8
0.7
0.6
Sample 1
0.5
Sample 2
0.4
Sample 3
Sample 4
0.3
Sample 5
0.2
Sample 6
0.1
0
Moisture, Karl Fisher (%Vol)
Methanol (%Vol)
0.6
0.5
Sample 1
0.4
Sample 2
Sample 3
0.3
Sample 4
0.2
Sample 5
ASTM 5798
0.1
0
Methanol (%Vol)
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

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