Pfa 2012

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Pfa 2012

  1. 1. 18 Fuel Properties Determined in 3 Minutesby Raman Spectroscopy Carl Brouillette, Frank Inscore, Michael Donahue, Stuart Farquharson, and Wayne SmithProviding Chemical Information When & Where You Need It Visit our Booth www.rta.biz
  2. 2. 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.
  3. 3. Current Capability 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 Million3
  4. 4. Concept Overview: Portable Fuel Analyzer Operation: • No Sample Preparation • 3-Minute Measurement • Portable (25 pounds) • Battery Powered (+AC adapter) • Rugged • Broad Temp Range • Wireless Comm. • Spill Resistant Analysis: • acidity • cetane index • alcohols • cloud point • aromatics • density • ether • distillation values • olefins • flash point • saturates • freeze point • sulfur • lubricity • net heat • octane rating • pour point • viscosity Red = critical properties4 Providing Chemical Information When & Where You Need It
  5. 5. Selecting a Technology: Vibrational SpectroscopyThe disadvantages usual decide which spectroscopy to use. Providing Chemical Information When & Where You Need It
  6. 6. Selecting a Raman: numerous peaks Technology:Vibrational Spectroscopy NIR: few, broad, overlapping peaks Infrared: few peaks Providing Chemical Information When & Where You Need It
  7. 7. Raman Spectra of Basic Fuels • •7 Providing Chemical Information When & Where You Need It
  8. 8. General Unknowns: Raman vs Near-Infrared Raman: Every spectrum is different NIR: peaks are not distinct, often not unique, and sometimes no peaks at all No peaks! No unique peaks!8
  9. 9. Fuels: Raman vs Near-Infrared Raman: different fuels NIR: all fuels look alike produce different spectra9
  10. 10. RTA Advantage: No Fluorescence Diesel Fuel All Other Raman Analyzers 785 nm Laser Excitation RTA 1064 nm Laser Excitation 785 nm excitation generates fluorescence and does not allow analysis. Providing Chemical Information When & Where You Need It10
  11. 11. RTA Advantage: No Wavenumber Shift 5.0 Dispersive Raman Analyzers change Diesel 2 wavenumber response with temperature: (±-8 cm-1) 2 cm-1 shift produces wrong values. 8 cm-1 shift produces wrong decisions! 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 Ram Shift, cm an -111 Providing Chemical Information When & Where You Need It
  12. 12. RTA’s Military Grade Portable Fuel Analyzer12
  13. 13. Validation of Ruggedness: Composite Wheeled Vehicle Vibration: 810F•13
  14. 14. Validation of Ruggedness: 26 Drop Tests: 810F14
  15. 15. How it Works: Basis for Correlations Raman Measures Chemical Composition, Chemical Composition Dictates Properties Raman Spectra Chemical Physical Composition Properties15 Providing Chemical Information When & Where You Need It
  16. 16. Density: Raman Spectral Correlations 6 Regression Coefficient 3 0 • -3 • Fingerprint Region CH Region -6 Raman Intensity Naphthene Stretch Alkane CH2 Stretch Wavenumbers (∆cm-1) Naphthalene, d=1.02 g/ml Cetane, d =0.77 g/ml16 Providing Chemical Information When & Where You Need It
  17. 17. Density: Raman Spectral Correlations 32 Jet Samples17
  18. 18. Density: ASTM-Raman Correlations Correlation = 0.985 Predicted Density (g/cm3) Raman Error = ±0.004 ASTM = ±0.0008 ALL FUELS Diesel 2 Correlated Jets Value Measured Value Measured Density (g/cm3) All fuel types (over 800 fuel samples)18 Providing Chemical Information When & Where You Need It
  19. 19. Sulfur: ASTM-Raman Correlations Correlation = 0.95 Correlation = 0.96 Raman Error = ±0.11 Raman Error = ±0.01 168 Diesels 75 ULSD Accurate ASTM data = smaller Raman error19 Providing Chemical Information When & Where You Need It
  20. 20. User Interface: 17 Properties20 Providing Chemical Information When & Where You Need It
  21. 21. User Interface: Designed for Customer Military Commercial or21 Providing Chemical Information When & Where You Need It
  22. 22. Software Architecture: Decision Tree Is it a fuel? Is it D -2, JP -5 or JP -8? Is it contaminated? ID contaminant Yes Yes Yes No No No Identify liquid ID fuel type Can I use as D-2, JP -5 or JP -8? YES Yes No Is it marginal? Provide critical properties Yes No NO22 Providing Chemical Information When & Where You Need It
  23. 23. User Interface: More Properties Raman NIR Diesel-2 Biodiesel-100 Sasol-Jet Hydraulic oil Gasoline Isopropyl Alcohol23 Providing Chemical Information When & Where You Need It
  24. 24. User Interface: Properties24
  25. 25. User Interface: More Properties Diesel-2 JP-8 or JP-525 Providing Chemical Information When & Where You Need It
  26. 26. 15 Unknown Samples All fuels correctly identified All properties Correct within error Two fuels correctly identified as marginal26 Providing Chemical Information When & Where You Need It
  27. 27. Validation of Analysis: SwRI Results 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.27 Marines with greater flexibility and more control of tactical and emergency situations.
  28. 28. 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%28 Providing Chemical Information When & Where You Need It
  29. 29. Providing Chemical Information When & Where You Need It Keeping the Military Moving29
  30. 30. RamanProIn-Process, Continuous Analysis! No Sample Preparation! • Fluorescence Free Raman • Analyzer Always Calibrated • Universal Interface • Industry Hardened
  31. 31. Real-Time Biodiesel BlendingAnalysisAnalysis that can be done:• Percent Biodiesel B100• Cetane Index B50• Cloud Point B20• Density B5• Distillation values• Flash point• Sulfur• Viscosity Raman Calibration Curve Precision ±1.5% Providing Chemical Information When & Where You Need It
  32. 32. Real-Time Synthetic Fuel Analysis Diesel 2 Sasol (FT) Diesel B100 BiodieselPetroleum, Synthetic, and Blends can be identified. Providing Chemical Information When & Where You Need It
  33. 33. Portable Fuel AnalyzerFuel Properties in 3 minutes! No Sample Preparation! • Cetane • Density • Lubricity • Acid # • Net Heat • Aromatics • Viscosity • Olefins • Cloud Pt • Saturates • Pour Pt • Sulfur • Flash Pt • Water • Freeze Pt • Distill Pts
  34. 34. RamanProIn-Process, Continuous Analysis! No Sample Preparation! • Fluorescence Free Raman • Analyzer Always Calibrated • Universal Interface • Industry Hardened

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