Pfa 2012
Transcript of Pfa 2012
18 Fuel Properties Determined in 3 Minutes by Raman Spectroscopy
Providing Chemical Information When & Where You Need It
Carl Brouillette, Frank Inscore,
Michael Donahue, Stuart Farquharson, and
Wayne Smith
www.rta.biz
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Need: Fuel, the most important supply
• The US Military consumes 300,000 gallons of fuel each day in Afghanistan.
• There are only 4 ground supply routes (e.g. Khyber Pass).
• Convoys are easy targets for road side bombs.
• 1 in 5 US casualties in Afghanistan is the result of protecting fuel and water convoys.
• The use of local fuel would reduce human
casualties costs, and increase combat unit mobility during operations.
• But local fuel must be free of adulterants
(sabotage) or contaminants and meet Critical Fuel Property Values.
Petroleum Quality Analysis System-Enhanced (PQAS-E)
• 16 Standard Tests • 2-3 hours (1-2 days for sample delivery) • BUT, can’t do adulterants or biofuels • Needs HVAC & Generator • $1.2 Million
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Current Capability
Concept Overview: Portable Fuel Analyzer Operation: • No Sample Preparation • 3-Minute Measurement • Portable (25 pounds) • Battery Powered (+AC adapter) • Rugged • Wireless Comm.
Analysis: • acidity • alcohols • aromatics • ether • olefins • saturates • sulfur
• cetane index • cloud point • density • distillation values • flash point • freeze point • lubricity • net heat • octane rating • pour point • viscosity
• Broad Temp Range
Red = critical properties 4
• Spill Resistant
Providing Chemical Information When & Where You Need It
The disadvantages usual decide which spectroscopy to use.
Providing Chemical Information When & Where You Need It
Selecting a Technology: Vibrational Spectroscopy
Providing Chemical Information When & Where You Need It
Selecting a Technology:
Vibrational Spectroscopy
Raman: numerous peaks
Infrared: few peaks
NIR: few, broad, overlapping peaks
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No peaks!
No unique peaks!
Raman: Every spectrum is different
NIR: peaks are not distinct, often not unique, and sometimes no peaks at all
General Unknowns: Raman vs Near-Infrared
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Raman: different fuels produce different spectra NIR: all fuels look alike
Fuels: Raman vs Near-Infrared
All Other Raman Analyzers 785 nm
Laser Excitation
RTA 1064 nm
Laser Excitation
Diesel Fuel
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785 nm excitation generates fluorescence and does not allow analysis.
RTA Advantage: No Fluorescence
Providing Chemical Information When & Where You Need It
5.0
Raman Shift, cm-11700700 800 900 1000 1100 1200 1300 1400 1500 1600
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Diesel 2 (±-8 cm-1)
Dispersive Raman Analyzers change wavenumber response with temperature: 2 cm-1 shift produces wrong values. 8 cm-1 shift produces wrong decisions!
RTA Advantage: No Wavenumber Shift
How it Works: Basis for Correlations Raman Measures Chemical Composition, Chemical Composition Dictates Properties
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Chemical Composition
Physical Properties
Raman Spectra
Providing Chemical Information When & Where You Need It
• •
Naphthalene, d=1.02 g/ml Cetane, d =0.77 g/ml
Wavenumbers (∆cm-1)
Fingerprint Region CH Region
Naphthene Stretch
Alkane CH2 Stretch
Ram
an In
tens
ity
Reg
ress
ion
Coe
ffici
ent 6
3
0
-3
-6
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Density: Raman Spectral Correlations
Providing Chemical Information When & Where You Need It
Pred
icte
d D
ensi
ty (g
/cm
3)
Measured Density (g/cm3) All fuel types (over 800 fuel samples)
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Correlation = 0.985 Raman Error = ±0.004 ASTM = ±0.0008 ALL FUELS
Jets
Diesel 2
Measured Value
Correlated Value
Density: ASTM-Raman Correlations
Providing Chemical Information When & Where You Need It
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Sulfur: ASTM-Raman Correlations
Correlation = 0.95 Raman Error = ±0.11 168 Diesels
Correlation = 0.96 Raman Error = ±0.01 75 ULSD
Accurate ASTM data = smaller Raman error
Providing Chemical Information When & Where You Need It
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or
Military
User Interface: Designed for Customer Commercial
Providing Chemical Information When & Where You Need It
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Software Architecture: Decision Tree
Is it a fuel? Is it D - 2, JP - 5 or JP - 8? No
ID contaminant Yes No
Yes
Identify liquid ID fuel type
Is it marginal?
Is it contaminated? No
Can I use as D - 2, JP - 5 or JP - 8?
Yes
Yes YES
Provide critical properties
No
NO No
Yes
Providing Chemical Information When & Where You Need It
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User Interface: More Properties
Providing Chemical Information When & Where You Need It
Diesel-2
Biodiesel-100
Sasol-Jet
Hydraulic oil
Gasoline
Isopropyl Alcohol
Raman NIR
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Diesel-2 JP-8 or JP-5
User Interface: More Properties
Providing Chemical Information When & Where You Need It
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15 Unknown Samples
All fuels correctly identified
All properties Correct within error
Two fuels correctly identified
as marginal
Providing Chemical Information When & Where You Need It
Validation of Analysis: SwRI Results
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Repeatability: “we found the measurement repeatability of the PFA to be very good, and in many cases, better than the ASTM repeatability.” Accuracy: “the accuracy of the PFA was in good agreement with the ASTM measurements. The exceptions were primarily in the estimation of density and viscosity, for which ASTM methods give extreme accuracy.” Hot & Cold: “It was also found that the cold and hot temperature measurements provided virtually the same repeatability and accuracy.” Go /No-Go: “In terms of go / no-go determinations, the PFA correctly rejected the five other fluids. The PFA also correctly identified the diesel and jet fuels by type (diesel, JP-5, or JP-8)” Ease-of-use: “the PFA was very easy to use and each sample was measured in 2-3 minutes, whereas the battery of ASTM measurements to determine the same properties requires as much as 2-3 hours. In summary, for its intended use, the PFA provided sufficient repeatable and accurate determination of fuel properties to provide a go / no-go determination for use of unknown fuels over the measured temperature range and would provide the U.S. Marines with greater flexibility and more control of tactical and emergency situations.
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Summary The Portable Fuel Analyzer can Automatically Identify:
Every common fuel: • 7 Critical Properties for Diesels and Jets • 10 Additional Properties
Numerous Other Chemicals as Unknowns • Over 50 common petroleum products (lubricants, etc.) • Every common solvent (including water) • Over 500 general chemicals (including explosives) • Chemical contaminants at < 1% • Petroleum contaminants at < 5%
• Biodiesel at < 2%
Providing Chemical Information When & Where You Need It
RamanPro In-Process, Continuous Analysis! No Sample Preparation!
• Fluorescence Free Raman • Analyzer Always Calibrated • Universal Interface • Industry Hardened
Real-Time Biodiesel BlendingAnalysis
Providing Chemical Information When & Where You Need It
• Percent Biodiesel • Cetane Index • Cloud Point • Density • Distillation values • Flash point • Sulfur • Viscosity
B100 B50 B20 B5
Analysis that can be done:
Raman Calibration Curve Precision ±1.5%
Real-Time Synthetic Fuel Analysis
Diesel 2 Sasol (FT) Diesel B100 Biodiesel
Petroleum, Synthetic, and Blends can be identified. Providing Chemical Information When & Where You Need It
Portable Fuel Analyzer Fuel Properties in 3 minutes!
No Sample Preparation!
• Cloud Pt • Pour Pt • Flash Pt • Freeze Pt • Distill Pts
• Cetane • Density • Lubricity • Net Heat • Viscosity
• Acid # • Aromatics • Olefins • Saturates • Sulfur • Water