determining the ethanol content of denatured fuel ethanol using … · 2018. 7. 26. · global...
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Gulf Coast Conference
Patrick Ritz
PAC LP
Determining the Ethanol Content of Denatured
Fuel Ethanol Using Near Infrared
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Global Ethanol Use
• Consumption of fuel-grade ethanol is on the rise
• Produced from bio- or renewable sources
• Advantages of Using Ethanol as Fuel or Fuel
Additive
– Imparts high octane in relation
to its cost
– Its molecule is 35% oxygen
• Aids in engine combustion
• Lowers harmful emissions
– Alternative to petroleum-based
components
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ASTM D4806 - Standard Specification for Denatured Fuel Ethanol
for Blending with Gasoline for Use as Automotive Spark-Ignition
Engine Fuel
• Ethanol Concentration by D5501
– GC Analysis
– Ethanol concentration determined from 93 to 97% (m/m).
• Proposal to Expand Scope (from 93-97% to 20-99%).
– Methanol concentration determined 0.1 to 0.6% (m/m).
• Water Concentration by ASTM E203 (volumetric Karl Fischer
titration) and E1064 (coulometric KF titration).
ASTM D4806
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GC Analysis • Good resolution between ethanol and methanol
• Good accuracy and precision with detailed information about the denaturant composition
• No information about water concentration
• Not suitable for portable field use
• Not a fast analysis
• Trained analyst
KF Analysis • Good accuracy at low concentration
• No information about ethanol concentration
• Hazardous materials used for the titration
– Chemical exposure risk
– Disposal of spent titration chemicals
• Some instrument and sample preparation required
• Trained analyst
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• Portable and rugged design allows ethanol analysis ‘in the Field’
• Highly accurate analysis results in less than 20 seconds
• Fully automated, easy to use
• Low cost (investment, operation, maintenance)
• (QuickSpec™) Delivered fully calibrated for 0% to 100% Ethanol & 0.01% - 5% water
Alternative – Near IR
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Portable IR Can Expand Range of
Testing
Carbon Dioxide
Fuel
Ethanol
Ethanol Fermentation
The atmosphere or recovery facility
Distillation
Molecular
Sieve
Denaturant
Ethanol Storage
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• Ethanol Producers – Process Monitoring
• Terminals – Fuel Ethanol and Oxygenated Gasoline Verification
• Independent Testing Labs
• Government Compliance Agencies
• Ethanol/Gasoline End-users: – Car Manufacturers
– Military
Users Needing Quick and Simple
Analysis
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NIR Technology
• Detection Method: Near
Infrared Spectroscopy
– Highly accurate
– Uses light to probe a
denatured ethanol sample
• Optical Design:
LED/Bandpass Filter
Photometric Technique
– Measures absorbance at
selected wavelengths
– 1950 nm / 1550 nm
Denatured Ethanol
5 mm Cell Pathlength
-0.5
0
0.5
1
1.5
2
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
NanometersA
bso
rban
ce
H2O
0.4 Vol.%
Ethanol
97.1 Vol.%
Distinct differences between ethanol and water absorption peaks
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NIR Ethanol Calibration
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NIR Water Calibration
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Independent Laboratory Data
Ethanol Conc.
@ 97.0 vol.%r R Rxy
QuickSpec 0.33 0.56
D5501 0.20 0.410.69
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Independent Laboratory Data
Water Conc.
@ 0.50 vol.%r R Rxy
QuickSpec 0.018 0.031
E1064 0.020 0.0860.091
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Independent Laboratory Data
Ethanol Conc.
@ 10.0 vol.%r R Rxy
QuickSpec 0.27 0.32
D5599 0.23 1.581.61
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Product Overview – Scope
Ethanol
Vol%
Water
Vol%
GC D5501
NIR*
@97 vol.%
KF
E203
KF
E1064
@0.5 vol.%
NIR*
@0.5 vol.%
Method Range 93% -97% 0% – 100% >0.05% 0% - 2% 0.01% - 5.0%
Repeatability 0.21% 0.33% 0.008% 0.020% 0.018%
Reproducibilty 0.53 0.56% 0.027% 0.086% 0.031%
*Internal RR at 95% confidence limit.
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• Near IR – Good accuracy and precision – Correlates to standard methods
– Measures ethanol and water (denaturant by difference)
– Can be made to be portable and rugged. Used where critical decisions are made.
– Low cost
– Simple to use
– Quick analysis with high throughput
Summary
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Thank you
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