Bio-SPK Research Report 2010 v5

Evaluation of Bio-Derived Synthetic Paraffinic Kerosenes (Bio-SPKs) PAGE 1 of 137 Version 3.0

Evaluation of Bio-Derived Synthetic Paraffinic Kerosenes (Bio-SPKs)

REPORT

Version 5.0

Prepared by

The Boeing Company UOP

United States Air Force Research Laboratory

May 2010


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Evaluation of Bio-Derived Synthetic Paraffinic Kerosenes (Bio-SPKs)

Executive Summary In 2009 a new ASTM specification (D7566-09, Standard Specification for Aviation Turbine Fuel Containing Synthesized Hydrocarbons) was developed for aviation turbine fuels. Contained in the D7566-09 specification is a specification for a synthetic paraffinic kerosene (SPK) blend component made from synthesis gas using the Fischer-Tropsch process commonly referred to as FT-SPK. Also contained in the D7566-09 specification is a specification for a blend of SPK with conventional petroleum based jet fuel. The specification allows for a maximum of a 50% blend of SPK with conventional jet fuel. Its the intent of this report to demonstrate that a suitable SPK can be produced from a bio-derived source (Bio-SPK) that can satisfy the requirements outlined in D7566-09. Further, its also the intent of this report to demonstrate that a 50% (v) Bio-SPK fuel blend with conventional petroleum jet fuel is suitable for use in turbine engines for commercial aviation. The report followed the guidelines outlined in the current version of ASTM D4054, Standard Practice for the qualification and Approval of new Aviation Turbine Fuels and Fuels Additives. Samples of Bio-SPK fuels were provided from six different fuel producers using a variety of feedstocks. The 100% and 50% (v) Bio-SPK fuels were compared to 100% and 50% (v) FT-SPK fuels using the same analytical method and plotted on the same graph whenever possible. FT-SPK fuel samples were produced by Sasol, Syntroleum, and Shell. In addition to the extensive amount of analytical fit-for purpose testing that was performed on both the Bio-SPK and FT-SPK neat and fuel blends the report includes engine ground test data using Bio-SPK fuel blends conducted by GE/CFM and Honeywell. The engine ground tests included performance, operability, and emission testing. Data obtained from three Bio-SPK test flights with Air New Zealand, Continental Airlines, and Japan Airlines are also included in this report. The fuel used for all three tests flights were a 50% (v) blend of Bio-SPK with conventional jet fuel (Jet A or Jet A-1).


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Table of Contents 1.0 Introduction ...................................................................................................................... 11

1.1 Objectives .................................................................................................................... 11 1.2 Approach...................................................................................................................... 12 1.3 Definitions.................................................................................................................... 14

1.3.1 Bio-SPK................................................................................................................... 14 1.3.2 Synthetic Paraffinic Kerosene (SPK) ...................................................................... 14 1.3.3 Fischer-Tropsch SPK (FT-SPK).............................................................................. 15 1.3.4 Bio-SPK Feedstock Definition ................................................................................ 15

1.3.4.1 Hydroprocessing FT Waxes and Renewable Fats and Oils to Produce SPK.. 16 1.3.4.2 Hydrotreating: Hydrogenation and Deoxygenation of FT Waxes and the Fatty Acid Derivatives in Animal Fats and Plant Oils .............................................................. 18 1.3.4.3 Cracking and Isomerization ............................................................................ 19 1.3.4.4 Fractionation ................................................................................................... 20

1.3.5 Process Overview of the Fuels Included in this Report........................................... 20 1.3.5.1 Energy & Environmental Research Center HRJ Process Description ............ 20 1.3.5.2 Syntroleum Bio-SPK Process Description...................................................... 20 1.3.5.3 UOP Bio-SPK Process Description ................................................................ 21

2.0 Data Analysis ................................................................................................................... 23 2.1 Relevance of the Comparative Evaluation of Semi-Synthetic Jet Fuels ...................... 24 2.2 Fuel Properties ............................................................................................................. 26

2.2.1 Chemistry................................................................................................................. 26 2.2.1.1 Hydrocarbon Chemistry.................................................................................. 26

2.2.1.1.1 Neat SPKs .............................................................................................................. 26 2.2.1.1.2 50% (v) SPK Blends............................................................................................... 29

2.2.1.2 Trace Materials ............................................................................................... 30 2.2.1.2.1 Neat SPKs .............................................................................................................. 31 2.2.1.2.2 50% (v) SPK Blends............................................................................................... 33

2.2.2 Bulk Physical and Performance Properties.............................................................. 34 2.2.2.1 Boiling Point Distribution............................................................................... 34


2.2.2.2 Vapor/Liquid Ratio ......................................................................................... 38 2.2.2.2.1 Neat SPKs .............................................................................................................. 38 2.2.2.2.2 50% (v) SPK Blends............................................................................................... 38

2.2.2.3 Thermal Stability ............................................................................................ 39 2.2.2.3.1 Neat SPKs .............................................................................................................. 39 2.2.2.3.2 50% (v) SPK Blends............................................................................................... 40

2.2.2.4 Lubricity and Response to Lubricity Improver............................................... 40 2.2.2.4.1 Neat SPKs .............................................................................................................. 40 2.2.2.4.2 50% (v) SPK Blends............................................................................................... 41

2.2.2.5 Viscosity vs. Temperature............................................................................... 41 2.2.2.5.1 Neat SPKs .............................................................................................................. 41 2.2.2.5.2 50% (v) SPK blends ............................................................................................... 42

2.2.2.6 Specific Heat vs. Temperature ........................................................................ 42 2.2.2.6.1 Neat SPKs .............................................................................................................. 44 2.2.2.6.2 50% (v) SPK Blends............................................................................................... 45

2.2.2.7 Density vs. Temperature ................................................................................. 45 2.2.2.7.1 Neat SPKs .............................................................................................................. 46 2.2.2.7.2 50% (v) SPK Blends............................................................................................... 46

2.2.2.8 Surface Tension vs. Temperature.................................................................... 47 2.2.2.8.1 Neat SPKs .............................................................................................................. 47


2.2.2.8.2 50% (v) SPK Blends............................................................................................... 48 2.2.2.9 Bulk Modulus vs. Temperature....................................................................... 48


2.2.2.10 Water Solubility vs. Temperature ................................................................... 50 2.2.2.10.1 Neat SPKs............................................................................................................. 50 2.2.2.10.2 50% (v) SPK Blends............................................................................................. 51

2.2.2.11 Solubility of Air .............................................................................................. 51 2.2.2.11.1 Neat SPKs............................................................................................................. 51 2.2.2.11.2 50% (v) SPK Blends............................................................................................. 52

2.2.3 Electrical Properties................................................................................................. 52 2.2.3.1 Dielectric Constant vs. Density....................................................................... 52


2.2.3.2 Electrical Conductivity and Response to Static Dissipator............................. 55 2.2.3.2.1 Neat SPKs .............................................................................................................. 55 2.2.3.2.2 50% (v) SPK Blends............................................................................................... 55

2.3 Properties Summary for Neat Bio-SPKs and FT-SPKs ............................................... 56 2.4 Properties Summary for 100% and 50% (v) Blended Bio-SPK and FT-SPK Fuels Compared to ASTM D7566-09................................................................................................. 57

2.4.1 Material Compatibility Studies................................................................................ 59 2.4.1.1 Material Compatibility of Synthetic Fuels...................................................... 59

2.4.1.1.1 Background ............................................................................................................ 59 2.4.1.1.2 Test Procedure........................................................................................................ 60 2.4.1.1.3 Test Results ............................................................................................................ 61

2.4.1.2 Additional Tests on SYN-R8 .......................................................................... 90 2.4.1.3 Additional Tests on UOP-x and UOP-xB50 SPKs ......................................... 91

2.4.1.3.1 Conclusions ............................................................................................................ 93 3.0 Additional Testing............................................................................................................ 95

3.1 Ground Handling / Safety ............................................................................................ 95 3.1.1 Effect on Clay Filtration .......................................................................................... 95 3.1.2 Filtration (SAE J1488)............................................................................................. 95 3.1.3 Storage Stability ...................................................................................................... 96

3.1.3.1 Peroxides......................................................................................................... 96 3.1.3.2 Potential Gums................................................................................................ 97

3.1.4 Flammability Limits ................................................................................................ 97 3.1.5 Autoignition Temperature ....................................................................................... 98 3.1.6 Hot Surface Ignition Temperature ........................................................................... 98 3.1.7 Minimum Ignition Energy ....................................................................................... 98 3.1.8 Ignition Quality Test (IQT) ..................................................................................... 99

3.2 Cetane Index ................................................................................................................ 99 3.3 Toxicity ...................................................................................................................... 100

3.3.1 Toxicity Evaluation Requirements ........................................................................ 100 3.3.2 Reciprocal Calculation Procedure ......................................................................... 100 3.3.3 Applicability of GGV/RCP Approach to Bio-SPK ............................................... 101 3.3.4 Similar Mixture Approach..................................................................................... 102 3.3.5 Similar Mixtures .................................................................................................... 103 3.3.6 FT-SPK.................................................................................................................. 105 3.3.7 Summary................................................................................................................ 105

3.4 Engine Tests for Bio-SPK Program ........................................................................... 106 3.4.1 Introduction ........................................................................................................... 106 3.4.2 Engine and Combustion Rig Testing ..................................................................... 106


3.4.2.1 Honeywell ..................................................................................................... 106 3.4.2.1.1 131-9 APU Testing............................................................................................... 106 3.4.2.1.2 TPE331-10 Turboprop Testing............................................................................. 108 3.4.2.1.3 TFE731-5 Engine Testing .................................................................................... 110 3.4.2.1.4 TFE731-5 Combustor Rig Testing ....................................................................... 112 3.4.2.1.5 Atomizer Cold Bench Testing .............................................................................. 116

3.4.2.2 CFM 56-7B Engine Ground Test.................................................................. 118 3.4.2.2.1 Engine Operability and Performance ................................................................... 118 3.4.2.2.2 Emissions ............................................................................................................. 120

3.4.2.3 Rolls-Royce RB211-524G2-T Engine Ground Run ..................................... 125 3.4.3 Flight Tests on 50% (v) Bio-SPK Blends.............................................................. 126

3.4.3.1 Air New Zealand (ANZ) Test Flight............................................................. 128 3.4.3.1.1 Flight Crew Observations..................................................................................... 128 3.4.3.1.2 Post-Flight Data Analysis..................................................................................... 129

3.4.3.2 Continental Airlines (CAL) Test Flight ........................................................ 129 3.4.3.2.1 Prior to the Test Flight.......................................................................................... 130 3.4.3.2.2 Flight Crew Observations..................................................................................... 130 3.4.3.2.3 Post Flight Data Analysis ..................................................................................... 131

3.4.3.3 Japan Airlines (JAL) Test Flight................................................................... 132 3.4.3.3.1 Flight Crew Observations..................................................................................... 133 3.4.3.3.2 Post Flight Data Analysis ..................................................................................... 133

4.0 Conclusions and Recommendations............................................................................... 133 5.0 Acknowledgments .......................................................................................................... 134 6.0 References ...................................................................................................................... 135 List of Figures Figure 1-1. Overview: Fuel and Additive Approval Process........................................................................ 12 Figure 1-2. Test Program.............................................................................................................................. 13 Figure 1-3. Fischer-Tropsch Process and Hydrotreating/Hydrocracking Process ........................................ 14 Figure 1-4. Examples of C18 Fatty Acid Derivatives as Feeds for the HRJ Process..................................... 16 Figure 1-5. Comparison of Processes to Produce SPK................................................................................. 17 Figure 1-6. Competing Deoxygenation Mechanisms for the Production of n-Paraffins .............................. 19 Figure 1-7. Bio-SynfiningTM SPK Process ................................................................................................... 21 Figure 1-8. Simplified Overview of the UOP Process to Produce HRJ SPK ............................................... 22 Figure 2-1. Carbon Chemistry of Neat FT and Bio-SPKs. ........................................................................... 28 Figure 2-2. Carbon Chain Distribution of Neat Bio-SPK Samples .............................................................. 29 Figure 2-3. BP Distribution of SPK Fuels by D2887 ................................................................................... 35 Figure 2-4. BP Distribution of Neat SPKs.................................................................................................... 36 Figure 2-5. BP Distribution of SPK Blends.................................................................................................. 36 Figure 2-6. Vapor Pressure vs. Temperature of Neat SPKs ......................................................................... 38 Figure 2-7. Vapor Pressure vs. Temperature of 50% (v) SPK blends .......................................................... 38 Figure 2-8. Lubricity of Neat SPKs and Response to CI/LI ......................................................................... 40 Figure 2-9. SPKs Response to CI/LI Additives............................................................................................ 41 Figure 2-10. Temperature Dependence of the Kinematic Viscosity for Neat Bio-SPKs.............................. 41 Figure 2-11. SPK Blends Viscosity vs. Temperature ................................................................................... 42 Figure 2-12. Temperature Dependence of the Specific Heat Capacity of Neat SPKs .................................. 44 Figure 2-13. SPK Blends Specific Heat Capacity ........................................................................................ 45 Figure 2-14. Neat Bio-SPKs Density vs. Temperature................................................................................. 46 Figure 2-15. SPK B50 Blends Density vs. Temperature .............................................................................. 46 Figure 2-16. Density vs. Temperature Graphs.............................................................................................. 47 Figure 2-17. Surface Tension vs. Temperature of Neat SPKs...................................................................... 47 Figure 2-18. Surface Tension Characteristics of SPK Blends ...................................................................... 48 Figure 2-19. Isothermal Tangent Bulk Modulus vs. Temperature for Neat SPKs........................................ 49 Figure 2-20. Isothermal Tangent Bulk Modulus vs. Temperature for SPK Blends...................................... 49 Figure 2-21. Neat Bio-SPKs, Water Solubility vs. Temperature.................................................................. 50


Figure 2-22. 50 % (v) Bio-SPK Blends, Water Solubility vs. Temperature................................................. 51 Figure 2-23. Neat Bio-SPKs, Solubility of Air @ 14.7 PSI (1 atm)............................................................. 52 Figure 2-24. 50% (v) Bio-SPK Blends, Solubility of Air @ 14.7 PSI (1 atm) ............................................. 52 Figure 2-25. Neat SPK, Dielectric Constant K vs. Temperature .................................................................. 53 Figure 2-26. Neat SPK, Density vs. Dielectric Constant K .......................................................................... 53 Figure 2-27. 50% (v) SPK Blends, Dielectric Constant K vs. Temperature................................................. 54 Figure 2-28. 50% (v) SPK Blends, Density vs. Dielectric Constant K......................................................... 54 Figure 2-29. Neat SPK, Electrical Conductivity and Response to Static Dissipator .................................... 55 Figure 2-30. 50% (v) SPK Blends, Electrical Conductivity and Response to Static Dissipator................... 55 Figure 2-31. Tensile Strength Results for the Nitrile Bladder Innerliner ..................................................... 63 Figure 2-32. Elongation Results for the Nitrile Bladder Innerliner .............................................................. 65 Figure 2-33. Volume Swell Results for the Nitrile Bladder Innerliner......................................................... 65 Figure 2-34. Tensile Strength Results for the AMS-S-8802 Polysulfide Sealant......................................... 72 Figure 2-35. Elongation Results for the AMS-S-8802 Polysulfide Sealant.................................................. 72 Figure 2-36. Volume Swell Results for the AMS-S-8802 Polysulfide Sealant ............................................ 72 Figure 2-37. Shore A Hardness Results for the AMS-S-8802 Polysulfide Sealant ...................................... 73 Figure 2-38. Peel Strength Results for the AMS-S-8802 Polysulfide Sealant.............................................. 73 Figure 2-39. Tensile Strength Results for the AMS 3277 Polythioether Sealant ......................................... 76 Figure 2-40. Elongation Results for the AMS 3277 Polythioether Sealant .................................................. 76 Figure 2-41. Volume Swell Results for the AMS 3277 Polythioether Sealant............................................. 77 Figure 2-42. Shore A Hardness Results for the AMS 3277 Polythioether Sealant....................................... 77 Figure 2-43. Peel Strength Results for the AMS 3277 Polythioether Sealant .............................................. 77 Figure 2-44. O-ring Swell Test R-8........................................................................................................... 90 Figure 2-45. O-ring Tensile Strength R-8................................................................................................... 90 Figure 3-1. Peroxide Formation, SPK Blends .............................................................................................. 97 Figure 3-2. a) 131-9 APU Installed in Test Cell, b) Mobile Emissions Truck, c) Fuel Drums .................. 107 Figure 3-3. 131-9 Exhaust Emissions Relative to Baseline Fuel................................................................ 108 Figure 3-4. TPE331-10 Turboprop Installed in Test Cell........................................................................... 109 Figure 3-5. TPE331-10 Emissions Relative to Baseline Fuel..................................................................... 110 Figure 3-6. TFE731-5 Engine Installed in San Tan Test Cell .................................................................... 111 Figure 3-7. Portable Fuel Tanks at San Tan Test Site ................................................................................ 111 Figure 3-8. TFE731-5 Combustor Rig Installed in C-100 Test Cell .......................................................... 113 Figure 3-9. TFE731-5 Rig Gaseous and Smoke Emissions........................................................................ 113 Figure 3-10. TFE731-5 Rig Lean Blowout Results .................................................................................... 114 Figure 3-11. TFE731-5 Rig Lean Ignition Results ..................................................................................... 115 Figure 3-12. TFE731-5 Rig Lean Ignition Results for Cold Fuel............................................................... 115 Figure 3-13. Comparison of Atomizer Spray Droplet Size ........................................................................ 117 Figure 3-14. Comparison of Atomizer Cold (-40oC) Spray for JP-8 and Biofuel Blend............................ 117 Figure 3-15. Emissions Set-up.................................................................................................................... 120 Figure 3-16. H/C Molar Ratios for Baseline Jet A, Neat Bio-SPK, and Blends of the Two ...................... 121 Figure 3-17. LTO Emissions and Maximum Smoke Number for Test Blends as % Difference from Jet A for Lowest (18K) and Highest (27K) CFM56-7B Engine Ratings............................................................. 122 Figure 3-18. LBO Historical Data Comparison.......................................................................................... 123 Figure 3-19. Warm Start Comparison ........................................................................................................ 124 Figure 3-20. Cold Start Comparison........................................................................................................... 124 Figure 3-21. Accel Time Comparison ........................................................................................................ 125 Figure 3-22. Engine Ground-run Data is Shown from a RR RB211-524G2-T Engine Taken at Auckland on Dec. 30, 2008.............................................................................................................................................. 125 Figure 3-23. Flight Test Program ............................................................................................................... 127 Figure 3-24. Air New Zealand 747-400 Flight Test Profile and Events During the Flight Test ................ 129 Figure 3-25. Continental Airlines 737-800 Flight Test Profile on January 7, 2009 ................................... 130 Figure 3-26. Cruise Snapshots for Previous Continental Airlines 737-800 Flight and Biofuel Flight ....... 132 List of Tables Table 1-1. Examples of the Fatty Acid Distribution of Different HRJ Feedstocks ...................................... 18


Table 2-1. Identification of the Bio-SPK Jet Fuels Tested ........................................................................... 23 Table 2-2. From ASTM D7566: Detailed Requirements of Aviation Turbine Fuels Containing Synthesized Hydrocarbons, TABLE 1, Part 1 .................................................................................................................. 24 Table 2-3. From ASTM D7566: Detailed Requirements of Aviation Turbine Fuels Containing Synthesized Hydrocarbons, TABLE 1, Part 2 .................................................................................................................. 25 Table 2-4. From ASTM D7566: Detailed Batch Requirements; Hydroprocessed SPK, TABLE A1.1........ 25 Table 2-5. From ASTM D7566: Other Detailed Requirements; Hydroprocessed SPK, TABLE A1.2........ 25 Table 2-6. Method Cross-Comparison of Hydrocarbon Types for a Camelina Derived SPK...................... 26 Table 2-7. Breakdown of Hydrocarbon Types for Neat SPK Jet Fuels ........................................................ 27 Table 2-8. Analysis of Neat SPK Samples. .................................................................................................. 28 Table 2-9. ASTM-D5291 Analysis of Neat SPK Samples ........................................................................... 29 Table 2-10. Hydrocarbon Chemistry of B50 Fuels....................................................................................... 29 Table 2-11. Hydrocarbon Types by ASTM D2425 ...................................................................................... 30 Table 2-12. Organic Trace Materials............................................................................................................ 30 Table 2-13. Chemical Analysis of Neat Bio-SPK Jet Fuels ......................................................................... 31 Table 2-14. Metal Analysis by ICP of Neat SPK Jet Fuels by UOP Method 389 ........................................ 32 Table 2-15. Metal Analysis by ASTM D7111 of Neat SPK Jet Fuels.......................................................... 32 Table 2-16. Trace Components in the B50 SPK Jet Fuels............................................................................ 33 Table 2-17. Metal Analysis by ICP of the B50 Bio-SPK Jet Fuels .............................................................. 33 Table 2-18. Principal Elements Detected in Jet Fuels from US Navy Technical Report No. 1845 .......... 34 Table 2-19. Slope of the Boiling Point Curves for Neat SPKs..................................................................... 34 Table 2-20. Calculated D86 Values from D2887 Data for Neat Bio-SPKs.................................................. 35 Table 2-21. Actual D86 Results for 100% SPK Fuels.................................................................................. 35 Table 2-22. Slope of the Boiling Point Curves for 50% (v) SPK Blends ..................................................... 37 Table 2-23. BP Distribution of B50 SPK Blend Samples per ASTM D86................................................... 37 Table 2-24. BP Distribution of B100 and B50 Bio-SPK and Jet A-1 per ASTM D86................................. 37 Table 2-25. Fuel Thermal Stability Tests of Neat Bio-SPKs and FT-SPKs ................................................. 39 Table 2-26. Thermal Stability of Bio-SPK 50% (v) Jet Fuel Blends............................................................ 40 Table 2-27. Reversing Cp for Neat SPKs..................................................................................................... 44 Table 2-28. Reversing Cp for Blended SPKs ............................................................................................... 45 Table 2-29. Speed of Sound in the SPKs...................................................................................................... 50 Table 2-30. Neat Bio-SPKs Properties Against Fuel Specifications ............................................................ 56 Table 2-31. Comparison with Data from Table A1 from D7566, Detailed Requirements of Aviation Turbine Fuels Containing Synthesized Hydrocarbons ................................................................................. 57 Table 2-32. Comparison with Data from Table A1 from D7566, Detailed Requirements of Aviation Turbine Fuels Containing Synthesized Hydrocarbons, Contd .................................................................... 58 Table 2-33. Fuels Used for Fluid Immersions .............................................................................................. 59 Table 2-34. Adhesives .................................................................................................................................. 62 Table 2-35. Nitrile Bladder Innerliner .......................................................................................................... 64 Table 2-36. Polyurethane Bladder Inner Liner ............................................................................................. 66 Table 2-37. Self-Sealing Bladder Material ................................................................................................... 66 Table 2-38. Coatings .................................................................................................................................... 67 Table 2-39. AMS-S-4383 Nitrile Coating .................................................................................................... 68 Table 2-40. Dichromate Cured AMS-S-8802 Polysulfide Sealant ............................................................... 69 Table 2-41. Manganese Dioxide Cured AMS-S-8802 Polysulfide Sealant.................................................. 70 Table 2-42. Manganese Dioxide Cured AMS-S-8802 Polysulfide Sealant, Contd..................................... 71 Table 2-43. AMS 3375 Fluorosilicone Sealant ............................................................................................ 74 Table 2-44. AMS 3379 Polyurethane Sealant .............................................................................................. 75 Table 2-45. AMS 3277 Polythioether Sealant .............................................................................................. 78 Table 2-46. AMS 3281 Low-Density Polysulfide Sealant ........................................................................... 79 Table 2-47. Noncuring Groove Sealants ...................................................................................................... 80 Table 2-48. Foam ......................................................................................................................................... 80 Table 2-49. Composites................................................................................................................................ 81 Table 2-50. Nitrile O-ring (AMS-P-5315).................................................................................................... 82 Table 2-51. Fluorosilicone O-ring (AMS-R-25988)..................................................................................... 83 Table 2-52. Fluorocarbon GLT O-ring (AMS-R-83485) ............................................................................. 84


Table 2-53. Fluorocarbon O-ring (AMS 7276) ............................................................................................ 85 Table 2-54. Acrylic/Nitrile Hose .................................................................................................................. 86 Table 2-55. Epichlorohydrin Hose ............................................................................................................... 87 Table 2-56. Wire Insulations ........................................................................................................................ 88 Table 2-57. Potting Compound .................................................................................................................... 89 Table 2-58. Sealant BMS5-45 Immersion Test for Neat UOP-3 Bio-SPK................................................... 91 Table 2-59. Elastomer Compatibility Testing: Primary Elastomer Tests for Neat UOP-3 Bio-SPK ........... 91 Table 2-60. Elastomer Compatibility Testing: Primary Elastomer Tests for Neat UOP-3 Bio-SPK ........... 92 Table 2-61. Materials Compatibility UOP-4 ................................................................................................ 92 Table 2-62. Materials Compatibility Comparison, UOP-4, Jet A Fuels ....................................................... 92 Table 2-63. UOP-2B50 Blend, Elastomer Compatibility ............................................................................. 93 Table 2-64. UOP-4B50 Blend, Elastomer Compatibility ............................................................................. 93 Table 3-1. SPK Neat and Blends, Effect on Clay Filtration ......................................................................... 95 Table 3-2. Removal of Emulsified Free Water for SAS-IPK (FT-SPK) ...................................................... 95 Table 3-3. Removal of Emulsified Free Water for UOP-2B50 (Bio-SPK 50% (v) Blend) .......................... 96 Table 3-4. Removal of Emulsified Free Water for Different Fuels SAE J1488 ........................................ 96 Table 3-5. SPK, Neat and Blends, Potential Gum per ASTM D5304 .......................................................... 97 Table 3-6. SPK Neat and Blends, Flammability Limits per ASTM E681.................................................... 97 Table 3-7. SPK Neat and Blends, Autoignition Temperature Test per ASTM E659 ................................... 98 Table 3-8. Hot Surface Ignition Temperature, FTN791-6053...................................................................... 98 Table 3-9. Minimum Ignition Energy, E582 ................................................................................................ 98 Table 3-10. Ignition Quality Test (IQT), D6890 .......................................................................................... 99 Table 3-11. Cetane Index for SPKS, Neat or Blended Jet Fuels .................................................................. 99 Table 3-12. Hydrocarbon Class OELs........................................................................................................ 100 Table 3-13. Group Guidance Values .......................................................................................................... 101 Table 3-14. Occupational Exposure Limit Based on GGV/RCP Method. ................................................. 102 Table 3-15. Isoparaffinic Hydrocarbon Solvents Reviewed by Mullin et al. ............................................. 103 Table 3-16. Toxicity Data for Isoparaffinic Solvents and Jet Fuels ........................................................... 104 Table 3-17. Biofuel Blend Analysis at Honeywell, per ASTM D1655 ...................................................... 106 Table 3-18. Atomization Test Fluid Properties .......................................................................................... 116 Table 3-19. Energy Properties for the 50% Blended Fuels, Compared to Nominal Jet Fuel...................... 119


1.0 Introduction Historically, nearly all of the aviation fuel used in aviation turbine engines has been produced from crude petroleum feedstocks. Aviation turbine fuel is often referred to as kerosene or, in general, jet fuel. The crude oils are processed in a refinery to make a host of useful products; including gasoline, diesel, jet fuel, petrochemicals, and asphalt components. Kerosene is produced as a straight run product but is also produced through hydroprocesses, especially from heavier crude oil feedstocks. Hydroprocesses are catalytic processes that convert part of the crude oil into a high quality hydrocarbon aviation fuel. Crude oil feeds can vary widely in terms of the amount of heavy components, heteroatom content, and metal content. The modern refinery uses hydroprocessing to process these different crude oil feeds to produce consistent, high quality fuels. Kerosene jet fuel is a hydrocarbon fuel composed almost entirely of hydrogen and carbon elements. The hydrocarbon composition consists mainly of paraffins (iso and normal), cycloparaffins (naphthenes), and aromatics1. Aviation jet fuel produced from different feeds and processes will have different ratios of these hydrocarbon components.

Synthetic Paraffinic Kerosene (SPK) made from hydroprocessing bio-derived fats and oils (Bio-SPK) or products from a Fischer-Tropsh reaction (F-T SPK) typically consists of normal and isoparaffin components with a relatively small amount of cycloparaffins. These same components are found in petroleum-derived aviation turbine fuels. Similarly to petroleum refining, the processes to produce SPK (FT-SPK or Bio-SPK) minimize the differences in the final product to produce a high quality fuel that can constantly meet the stringent requirements for aviation turbine fuel.

1.1 Objectives The objective of this document is to demonstrate that Synthetic Paraffinic Kerosene is a hydrocarbon fuel with properties indistinguishable from the paraffins found in petroleum kerosene. SPK is fully miscible with petroleum kerosene in any ratio. The data in this document will show that the SPK produced from renewable feedstocks (Bio-SPK) has the same properties as SPK produced through the gasification-Fischer-Tropsch synthesis process followed by hydroprocessing (FT-SPK). Both routes to SPK (FT-SPK and Bio-SPK) rely on hydroprocessing followed by fractionation as the final steps to produce highly branched paraffinic kerosene in the same boiling point range as petroleum derived jet fuel. In short, the objectives of this report are:

1. To compare the properties and characteristics of Bio-derived Synthetic Paraffinic Kerosenes (Bio-SPKs) to SPKs derived from syngas, also called Fischer-Tropsch SPKs (FT-SPKs).

2. To compare Bio-SPK/petroleum-based jet fuel blends to both FT-SPK/petroleum-based jet fuel blends and to conventional Jet A/Jet A-1, JP-5, JP-8 jet fuels.

3. Demonstrate that the process to produce Bio-SPKs is feedstock agnostic. 4. Demonstrate the suitability of Bio-SPKs made from a variety of feedstocks to be

used in commercial aviation up to a 50% (v) blend ratio.


1.2 Approach The approach used for completion of this report was to follow the recommended methodology detailed in the current ASTM D4054-092, Standard Practice for Qualification and Approval of New Aviation Turbine Fuels and Fuel Additives. The document was created with input from the engine and airframe OEMs as well others in the aviation industry. The document is based on previous experience and methodology used in past specification approvals. Figure 1-1 below from the revision of D4054 is a schematic of the overall qualification process for new fuels.

Figure 1-1. Overview: Fuel and Additive Approval Process

The test program is shown in more detail in Figure 1-2. The first step in qualification is to show that the new fuel meets specification properties. The second step is to show the fuel is fit-for-purpose by testing the fuels against the tests in the longer box, including chemical properties, bulk physical properties, and performance tests.


Figure 1-2. Test Program


1.3 Definitions

1.3.1 Bio-SPK The Bio-derived Synthetic Paraffinic Kerosene (Bio-SPK) jet fuels, or sometimes referred as Hydroprocessed Renewable Jet (HRJ) fuels are generally made in a two-step process. The first step is the deoxygenation of fatty acid esters and fatty acids. The second step is either an isomerization or a selective cracking and isomerization process. Bio-SPKs can be produced from bio-derived feedstocks such as animal fats and vegetable oils. The feedstock is defined in more detail later. The fatty acid derivatives in the feed are hydroprocessed to fully remove oxygen, saturate double bonds with hydrogen, crack paraffins into the jet range and isomerize paraffins to improve cold flow properties. This product is paraffinic kerosene composed of mostly branched paraffins in the kerosene boiling point range. It is the intent of this report to show that these Bio-SPK jet fuels are high quality jet fuels that can be considered as drop-in replacement fuels when blended up to 50% (v) with standard jet fuels.

1.3.2 Synthetic Paraffinic Kerosene (SPK) SPK is a paraffin fuel in the jet fuel boiling point range. SPK can be produced from products of gasification-Fischer-Tropsch (FT) synthesis processes or from a highly refined animal fat or plant oil. Both feedstocks are hydroprocessed to completely remove heteroatoms to produce a highly purified hydrocarbon fuel. As illustrated in Figure 1-3, both Bio-SPKs and Fischer-Tropsch SPKs rely on similar processes.

Figure 1-3. Fischer-Tropsch Process and Hydrotreating/Hydrocracking Process


1.3.3 Fischer-Tropsch SPK (FT-SPK) A FT-SPK is a SPK produced from a feedstock derived through a gasification followed by a Fischer-Tropsch synthesis process. The feedstocks for the gasification route include coal, natural gas, or biomass. The carbon monoxide and hydrogen produced in the gasification process are combined to form a mixture of products in the Fischer Tropsch synthesis process, including n-paraffins, oxygenates, and alpha olefins. These products are either polymerized (alpha-olefins) or further processed by reacting with catalyst and hydrogen; these processes are collectively known as hydroprocessing. The oxygen and other heteroatoms are removed, olefins are saturated, long chain paraffins cracked or isomerized. The final step is fractionization to produce a SPK with suitable properties to be used in turbine engines.

1.3.4 Bio-SPK Feedstock Definition The feedstocks for the Bio-SPK process are composed of fatty acid derivatives - both fatty acids or fatty acid esters. These molecules have an oxygen functional group at one end and a long aliphatic chain hydrocarbon with variable amounts and locations of double bonds on the other. The majority of these fatty acids are attached to a glycerol backbone and are known as acylglycerols. Most of these are triacylglycerols or triglycerides, where three fatty acid chains are attached to the glycerol backbone through ester groups. Smaller amounts of diglycerides and monoglycerides are also present. Some feeds contain a percentage of free fatty acids (FFA) where the fatty acid chain ends in a carboxylic acid group rather than the glyceryl ester. Since all the double bonds, ester groups, and carboxylic acid groups are removed in the Bio-SPK process, all fatty acid derivatives lead to the same products: n-paraffins. These different types of fatty acid derivatives are exemplified in Figure 1-4 for fatty acid derivatives with 18 carbons per fatty acid chain. In this example the portion of the molecule that remains after deoxygenation to become an n-paraffin is highlighted in red. The figure begins with a fully saturated (no double bonds) free fatty acid known commonly as stearic acid. For the next derivative the acid group is replaced with a methoxy group becoming a fatty acid methyl ester, or FAME, commonly known as biodiesel. In the next derivative the saturated C18 fatty acid chains are bonded to a glycerol molecule to form a triglyceride. The next two derivatives have double bonds and are commonly known as oleic and linolenic acid respectively. The final example shows a variety of C18 fatty acids with different amounts of double bonds attached to a glycerol molecule. A diglyceride and monoglyceride are shown as the final two molecules. As the schematic shows, these features that form the different derivatives - amount of double bonds and type of oxygen functional group - are removed during the deoxygenation stage. This stage results in the same product, an n-paraffin. As described in a later section, the n-paraffin product has the same number of carbons as the original fatty acid chain or one carbon less depending on the deoxygenation mechanism.


OH

O

O

O

O

O

O

O

OH

O

Methyl stearate (FAME) (C18)

n-paraffin

Monoglyceride

OH

O

Oleic Acid (C18)

O

O

O

O

O

O

Oleic Acids (C18) in triglyceride structure

Deoxygenation

(Hydrotreating)

O HH

CO

OCH4

CH3CH3

H2Various Acids (C18) in triglyceride structure

O

O

O

OOH

Linolenic Acid (C18)

Diglyceride

O

O

OH

OH

O

O

CH3

Stearic Acid (C18)

Figure 1-4. Examples of C18 Fatty Acid Derivatives as Feeds for the HRJ Process

1.3.4.1 Hydroprocessing FT Waxes and Renewable Fats and Oils to Produce SPK

Hydroprocessing is a term describing catalytic processes that use hydrogen as a reactant to improve fuel quality and yields. Hydroprocessing consists of two main processes typically called hydrotreating and hydrocracking. In hydrotreating, hydrogen is used to saturate olefins and remove heteroatoms contaminants from hydrocarbons. The technology is used widely in petroleum refineries to remove primarily sulfur and nitrogen from petroleum feeds. At the more severe hydrocracking conditions, hydrogen is used to crack heavy components to fuel-range components. Hydrocracking increases the quality and yield of distillate fuels by cracking large molecules into the diesel and jet range. Hydroprocessing is also the key technology for the production of high quality SPK due to the saturation of the double bonds and the removal of heteroatoms resulting in a highly pure hydrocarbon fuel. As defined above SPK can be produced from both FT3 and Bio-


SPK feeds through similar hydroprocesses. A general comparison of the two hydroprocessing pathways is provided in Figure 1-5 to show how SPK is produced from different feeds using similar hydroprocessing technology.

Figure 1-5. Comparison of Processes to Produce SPK

In existing commercial gasification FT pathways (lower section of Figure 1-5), coal and natural gas are used as feeds to produce syngas, which after clean-up is converted to a waxy product through FT synthesis. The as-produced FT product contains mostly n-paraffins along with olefins and oxygenates. The olefins and oxygenates in FT wax are hydrotreated to produce saturated normal paraffins. However, hydrotreating alone produces a wide boiling point distribution containing molecules that are typically too large for jet fuel or SPK. Further hydroprocessing (hydrocracking/isomerization) followed by a fractionation is often required to produce a suitable jet fuel. The production of FT-derived kerosene-range isoparaffinic product also requires hydrocracking to convert long paraffins into the jet range followed by fractionation to remove light and heavy side products. The upper portion of Figure 1-5 shows that olefins present in pretreated animal fats and plant oils are also saturated in the deoxygenation, or hydrotreating, stage of the hydroprocessing unit to produce an n-paraffin rich product. The Bio-SPK process differs from the FT process here since the carbon distribution of the n-paraffins produced from most fats and oils is usually much narrower than that of the wax produced by FT synthesis. As a result, the deoxygenated product is in the diesel-range. Similar to the FT-SPK process further hydroprocessing is required in Bio-SPK process to produce jet range paraffins.

Hydroprocessing

Plant Oils Animal Fats

Biomass Coal

Natural Gas Carbon

Hydrogen Other

Gasification CO H 2

Fischer - Tropsch

n- Paraffins Alpha - olefins Oxygenates (Alcohols, Carbonyls, Carboxylic

Acids) Hydrotreating

OxygenRemoved

OlefinsSaturated

n-Paraffinsisomerized to improve cold-flowproperties

Large molecules cracked to jet range

Hydrotreating

Triglycerides (Esters)

Free Fatty Acids

(Carboxylic Acids) Isomerization/

SelectiveHydrocracking

n-paraffins(C15-C20)(C8-C22Future)

LightGases

Naphtha

ParaffinicKerosene

(FT SPK orHRJ SPK)

Fractionation

ParaffinicDiesel

(FT Dieselor HRDiesel)

Isomerization/Selective

Hydrocracking

n-paraffins(C11-C22

Distillate)(>C22 Wax)

Bio-SPK Route

FT Route

Pretreatment (Degumming/

Bleaching)


Because the final processing steps in both SPK pathways include hydroisomerization and hydrocracking of n-paraffins, the SPK produced from renewable feedstocks has properties similar to the paraffinic fuels produced by a gasification-FT route.

1.3.4.2 Hydrotreating: Hydrogenation and Deoxygenation of FT Waxes and the Fatty Acid Derivatives in Animal Fats and Plant Oils

The primary heteroatom in FT waxes, animal fats, and plant oils is oxygen. Many of these feedstocks also contain olefins in a range of concentrations dependent upon the FT process or source of animal fat and plant oil. A hydrotreating process can remove the oxygen in such feedstocks and saturate the double bonds to produce a product composed primarily of n-paraffins. Fischer-Tropsch waxes are composed predominantly of straight-chain hydrocarbons with various amounts of oxygenates and olefins4,5. The concentrations of olefins and oxygenates are dependent on the FT process and can therefore vary from about 1-10%. The oxygenates are predominantly alcohols with lesser amounts of carbonyls and carboxylic acids. The FT process also impacts the carbon chain length of the straight chain process to produce a carbon number range that can vary from C5 to greater than C22 (in a low temperature FT process).

The composition of animal fats and plant oils were described previously. The length of the fatty acid chains (carbon number) varies among feedstocks, as does the number and positions of double bonds (degree of unsaturation). These features are the key differentiators between different sources of pretreated feedstocks (e.g., Camelina versus Palm Oil). Almost all fatty acid chains have even numbered carbon chains. All the fatty acids contain oxygen atoms. Examples of the characteristics of some different feedstocks are shown in Table 1-1. Most natural oils have 18 carbons in the majority of fatty acid chains, with 16 carbons as the second most abundant fatty acid chain. Some oils also contain significant amounts of C20 and C22 carbon chain lengths.

Wt % Fatty Acid Composition Examples

8:0 10:0 12:0 14.0 16.0 18.0 18:1 18:2 18:3 20:0 20:1 20:2 20:3 22:0 Other Source

Feedstock Natural Oil Jatropha Curcas 20 7 41 31 Akintayo6

Jatropha Curcas 14.1-15.3 3.7-9.8

34.3-45.8

29.0-44.2 Gubitz et al.

7

Camelina Oil 5.3-5.6 2.3-2.7

14.0-16.9

13.516.5

34.9-39.7

1.2-1.5

15.1-15.8

1.7-2.0

1.3- 1.7

2.6- 3.0 Abramovic et al.

8

Camelina Oil 6 2 15 16 39 0 16 2 1 4 Abramovic et al.8 Algal Oil 22 5 49 10 12 1 1 UOP Data Yellow Grease 17 10 56 10 6 UOP Data Beef Tallow 6 26 31 31 2 0 0 0 0 0 3 Baileys9

Fatty Acid Prefix

Caproic

Caprylic

Capric

Lauric

Myristic

Palmitic

Stearic

Oleic

Linoleic

Linolenic

Arachidic

Gondoic

Eicosadienoic

Eicosatrienoic

Erucic

Table 1-1. Examples of the Fatty Acid Distribution of Different HRJ Feedstocks


When the SPK feeds, including FT paraffins, animal fats and plant oils are hydrotreated to paraffins, oxygen atoms are removed. In the case of fatty acid derivatives, the deoxygenation is known to occur through competing mechanisms: decarboxylation (DeCOx) and hydrodeoxygenation (HDO) as shown in Figure 1-6.

Figure 1-6. Competing Deoxygenation Mechanisms for the Production of n-Paraffins

One carbon is removed and lost in the DeCOx reaction producing COx and a paraffin chain with an odd number of carbon atoms. Hydrogen is a reactant in the hydrodeoxygenation pathway (shown to the right in Figure 1-5) to produce water and a long-chain paraffin with the same even number of carbons as found in the fatty acid chain of the feed. The glycerol portion of a TAG (triacylglycerol) molecule is converted to propane. The hydrogenation of the double bonds occurs independently of the deoxygenation mechanism to produce a hydrogen-saturated straight-chain paraffin product. The final paraffin product after hydrotreating has a carbon-number composition very similar to the paraffin distribution in the FT feed or the fatty acid carbon-number distribution of the starting animal fat or plant oil. Hydrotreating of FT products produces an n-paraffin product whose carbon chain length distribution is similar to the feed distribution. The feed distribution can vary widely depending on the FT process used, for example, a low temperature versus high temperature FT process. Hydrotreating of most plant oils and animal fats produces a narrower n-paraffin product distribution ranging from nC15-nC22 with the major peaks being nC17-nC18, a product in the diesel fuel range but too heavy for jet fuel. Further hydroprocessing is necessary to produce a jet range SPK. Since the normal paraffin products of hydrotreating FT paraffins, animal fats, and plant oils are straight chain paraffins too heavy for jet fuel, hydrocracking is also necessary to produce the final SPK product.

1.3.4.3 Cracking and Isomerization The production of Bio-SPK and FT-SPK requires selective hydrocracking of the n-paraffin product along with substantial isomerization to produce a SPK product with a

H2+

CatalystDeCOx HDO

Fatty Acid Derivative

n-ParaffinicProduct

CH3

CH3

CH3

OO

OO

OO

HO

OOCH 3

H 3C H 3 C

H 3 C H 3 C CH 3

CH3CH3CH3

H3C

H3C H3C

H3C H3C

CH 3 CH 3 CH 3

+ CO + CO 2

+

H2O+


carbon chain distribution of approximately C9-C15. This step is called selective cracking because overcracking will result in low yields to jet range paraffins and high yields of light ends (C1-C4) and naphtha (C5-C8), both outside the jet fuel range. Isomerization is also required to lower the freeze point.

1.3.4.4 Fractionation The final paraffinic product of the Bio-SPK and FT-SPK routes is fractionated to meet the boiling point distribution of SPK. The side products after fractionation include light (low carbon number) and diesel range paraffins. The main control to meet key SPK specification properties from different feedstocks is the severity of the selective hydrocracking/hydroisomerization stage and fractionation. This combination controls the distribution of paraffins in the SPK as well as the iso/normal ratio. The fraction cut will also control the freeze point and flash point of the final fuel.

1.3.5 Process Overview of the Fuels Included in this Report

1.3.5.1 Energy & Environmental Research Center HRJ Process Description

The Catalytic Hydrodeoxygenation and Isomerization (CHI) process developed by Energy & Environmental Research Center (EERC) uses commercially available petroleum-refining catalysts to convert triacylglyceride and/or free fatty acid feedstocks to an isoparaffinic-rich SPK. The CHI process comprises hydrodeoxygenation to yield normal paraffins, followed by isomerization and distillation to yield a jet fuel-grade SPK. Feedstocks converted to specification-compliant SPK products via the CHI process include oils from algae, camelina, canola, coconut, corn, crambe, cuphea, soy, waste yellow and brown grease, tallow and various mixtures of these.

1.3.5.2 Syntroleum Bio-SPK Process Description Bio-Synfining is a low capital cost process for producing high quality SPK from bio-renewable feeds such as fats, greases and algae oils. In Bio-Synfining, fatty acids and glycerides are converted to SPK in three steps. First, raw feedstocks are treated to remove catalyst contaminants and water. In the second step, fatty acid chains are transformed into n-paraffins in a hydrotreater. For most bio-oils, fats and greases, the hydrotreater liquid product has mainly a C15-C18 n-paraffin composition. In the third step of the process, these long straight-chain paraffins are hydrocracked into shorter branched paraffins. The hydrocracked products fall mainly in the kerosene boiling range.


Figure 1-7. Bio-SynfiningTM SPK Process

As shown in the schematic flow diagram of Figure 1-7, the Bio-Synfining configuration for SPK is a simple single-train hydroprocessing unit. Not shown in Figure 1-7 is feed pretreatment. Syntroleums pretreatment process removes 98+% of the metal and phosphorus contaminants from fats and greases. The pretreated bio-feed is combined with the hydrocracker effluent which acts as solvent/diluent for the exothermic hydrotreater reactions. After separation from hydrogen and light hydrocarbons, the reaction products are transferred to fractionation. Virtually all the hydrotreated fresh feed, the C15-C18 n-paraffins, ends up with the heavies recycled to the hydrocracker. The volumetric yield of SPK from bio-feed depends on severity of hydrocracking. The process co-products, Bio-LPG and naphtha, are marketable commodities.

1.3.5.3 UOP Bio-SPK Process Description The commercial development of UOPs process to produce Bio-SPK is still in progress and is available for commercial license. Two reaction stages are employed to produce a low freeze point Bio-SPK. A simplified block flow diagram of the process is provided in Figure 1-8.


Figure 1-8. Simplified Overview of the UOP Process to Produce HRJ SPK

In this process, pressurized feedstock is mixed with hydrogen and then sent to a catalytic deoxygenation, or hydrotreating reactor (R1) where the bio-renewable oil is saturated and completely deoxygenated. Conversion of feed is complete and the volumetric yield of deoxygenated hydrocarbon products is >100%. Selectivity to diesel boiling-range paraffin is very high. The primary deoxygenation reaction byproducts are propane, water and carbon dioxide. The effluent from R1 is immediately separated at reactor pressure to remove carbon dioxide, water and low molecular weight hydrocarbons. The resultant n-paraffin product is mixed with additional hydrogen gas and then routed to an integrated catalytic selective cracking/isomerization, or hydrocracking reactor, R2, wherein the diesel range normal paraffin feed is mildly cracked and isomerized to maximize the yield of jet range isoparaffins. The highly isomerized product is the key to achieving the stringent freeze point requirements of aviation turbine fuel. The cracked and isomerized product is separated from excess hydrogen. The liquid product is sent to the product recovery section of the process where distillation steps are employed to maximize the yield of SPK while still meeting specification properties. Also, this final step removes separate coproducts such as propane and naphtha. Depending on the severity of the R2 reactor, high value renewable diesel is also produced and separated in the distillation step.


2.0 Data Analysis The Bio-SPK fuels and the data were provided by Air Force Research Laboratory (AFRL), Boeing, Defense Advanced Research Projects Agency (DARPA), Energy & Environmental Research Center (EERC), ENEOS, NESTE Oil, Sasol, Syntroleum, UOP and The US Navy. Except otherwise specified, when talking about blends, it represents a mixture of 50-50 (vol. %) biofuel/petroleum-based jet fuel.

Manufacturer ID Number Feedstock Process Jet Fuel % (v) Biofuel or FT Blend EERC EER-1 Canola Bio-SPK / 100

ENE-1 Algae Bio-SPK / 100 ENEOS

ENE-1B50 Algae Bio-SPK Jet A-1 50 NESTE Oil NES-1 Palm Bio-SPK / 100

SAS-GTL-1 FT-GTL / 100 SAS-GTL-2 FT-GTL / 100 SAS-IPK FT / 100 SAS-GTL-1B50* FT-GTL Jet A 50 SAS-GTL-2B50* FT-GTL Jet A 50

Sasol

SAS-IPKB50* FT Jet A-1 50 SHE-SPK FT-GTL / 100 SHE-SPKB50M FT-GTL JP-8 50 Shell SHE-SPKB50M* FT-GTL JP-8 50 SYN-R-8 Tallow Bio-SPK / 100 SYN-R-8B50 Tallow Bio-SPK Jet A 50 SYN-R-8B50M Tallow Bio-SPK JP-8 50 SYN-R-8x Halophyte Bio-SPK / 100 SYN-S-8 FT / 100 SYN-S-8B50 FT Jet A 50

Syntroleum

SYN-S-8B50M* FT JP-8 50 UOP-1 Camelina Bio-SPK / 100 UOP-2 Camelina-Jatropha-Algae Bio-SPK / 100 UOP-3 Jatropha Bio-SPK / 100 UOP-4 Jatropha-Algae Bio-SPK / 100 UOP-2B50 Camelina-Jatropha-Algae Bio-SPK Jet A 50 UOP-3B50 Jatropha Bio-SPK Jet A-1 50 UOP-4B50 Jatropha-Algae Bio-SPK Jet A 50 UOP-5 Camelina Bio-SPK / 100 UOP-6 Coconut Bio-SPK / 100 UOP-7 Jatropha Bio-SPK / 100 UOP-8 Palm Bio-SPK / 100 UOP-9 Soy-1 Bio-SPK / 100 UOP-10 Soy-2 Bio-SPK / 100 UOP-11 Soy/Canola Bio-SPK / 100 UOP-12 Tallow Bio-SPK / 100 UOP-HRJ-5 Camelina Bio-SPK / 100 UOP-HRJ-5B50M Camelina Bio-SPK JP-5 50

UOP

UOP-SOL-1 Algae Bio-SPK / 100 *Data from CRC project # AV-2-04a FT-SPK 50% (v) blends approved FT-SPK

Table 2-1. Identification of the Bio-SPK Jet Fuels Tested


2.1 Relevance of the Comparative Evaluation of Semi-Synthetic Jet Fuels Just for comparison, all of the neat FT-SPK and Bio-SPK fuels used in this report were compared to the specifications of ASTM D1655-08a10, Standard Specification for Aviation Turbine Fuels (see Table 2-30). The neat and the 50% (v) FT-SPK and Bio-SPK blends used in this report (see Table 2-1) were compared to the property tables outlined in ASTM D7566-0911, Standard Specifications for Aviation Turbine Fuels Containing Synthesized Hydrocarbons (see below Table 2-2 through Table 2-5) for the up to 50% (v) SPK blends and the 100% SPKs. Data on each individual fuel will be provided in later sections. Many of the tests were performed by different independent laboratories. Most of the fit-for-purpose tests have been performed on the neat Bio-SPK fuels as well, even though the approval is only sought for 50-50% (v) Bio-SPK-Jet A/Jet A-1 blends. Also included in this report is data on FT-SPKs, displayed on the same graphs as the Bio-SPK samples. The majority of the data on FT-SPK fuels were run using the same test methods used for the Bio-SPKs so that the data could be compared directly. Otherwise the data were extracted from the CRC report No. AV-2-04a12, Comparative Evaluation of Semi-Synthetic Jet Fuels.

Table 2-2. From ASTM D7566: Detailed Requirements of Aviation Turbine Fuels Containing Synthesized Hydrocarbons, TABLE 1, Part 1


Table 2-3. From ASTM D7566: Detailed Requirements of Aviation Turbine Fuels Containing Synthesized Hydrocarbons, TABLE 1, Part 2

Table 2-4. From ASTM D7566: Detailed Batch Requirements; Hydroprocessed SPK, TABLE A1.1

Table 2-5. From ASTM D7566: Other Detailed Requirements; Hydroprocessed SPK, TABLE A1.2

The volume percent of Bio-SPK in the jet fuel blends was set to 50% (v). From the data obtained on neat and blended jet fuels, it is possible to estimate some of the properties of different synthetic fuel/petroleum-based jet fuel blends with different volume ratio13.


2.2 Fuel Properties

2.2.1 Chemistry

2.2.1.1 Hydrocarbon Chemistry The determination of the different hydrocarbon types per ASTM D242514 test method, using mass spectroscopy (MS), was done on the SPK samples. Eleven hydrocarbon types can be determined with this test method, including paraffins (normal and iso), non-condensed cycloparaffins, condensed dicycloparaffins, condensed tricycloparaffins, alkylbenzenes, indanes or tetralins, or both, CnH2n-10 (indenes, etc.), naphthalenes, CnH2n-14 (acenaphthenes, etc.), CnH2n-16 (acenaphthylenes, etc.), and tricyclic aromatics. D2425 is a complicated method that was not originally developed for synthetic fuels. The fuel samples were sent to several independent laboratories for evaluation purpose. Some discrepancies were observed in the D2425 results. It is now believed that in D2425 test method, the isoparaffins content contributes to the cycloparaffins value due to a specific ion overlap. For comparison, some of the samples were analyzed by two different gas chromatography techniques, GC and GCxGC, and also by field ionization mass spectrometry (FIMS). The results are shown in Table 2-6.

GCxGC FIMS D2425 Analytical Method

wt. % vol. % vol. % Paraffins (n + iso) 92.29 91.70 75.80 Cycloparaffins 7.70 8.2 24.2 Aromatics 0.02 0.00 0.00

Table 2-6. Method Cross-Comparison of Hydrocarbon Types for a Camelina Derived SPK After some investigation, it was found that all the laboratories were not using the same calibration procedure and that it was impacting the results. A new calibration procedure appropriate for hydrocarbon analysis was subsequently proposed and is currently being validated. In the meantime, the reader should be aware that the cycloparaffins results for D2425 are anomalously high for SPK samples.

The aromatic content of the jet fuels was measured following ASTM D131915 test method using a glass adsorption column packed with activated silica and silica gel, containing fluorescent dyes. The hydrocarbons are separated in accordance with their adsorption affinities. Aromatic content could also be determined by High Performance Liquid Chromatography (HPLC) following ASTM D637916. High-resolution nuclear magnetic resonance (NMR), with 1H and 13C nuclei, was also used to determine the aromatic content, per ASTM D529217.

2.2.1.1.1 Neat SPKs Table 2-7 shows a compilation of the data obtained with the different methods described above.


UOP EER SAS SHE SYN Method Description Unit 1 2 3 4 HRJ-5 1 GTL-1 GTL-2 IPK SPK R-8 R-8x S-8 D 1319 Aromatics vol % 0.3 0.0 0.0 0.0 - 0.2 0# 0# 0.5 0.2# 0.0 0.7 0# D 5292, D2425, *D6379 Aromatics mass % 0.1 0.1 0.0 0.0


0

10

20

30

40

50

60

70

80

90

100

SAS-

GTL-1

*

SAS-

GTL-2

*

SAS-

IPK*

SHE-

GTL*

SYN-

S-8*

SAS-

GTL-1

SAS-

GTL-2

SHE-

GTL

SYN-

S-8

EER-

1

SYN-

R-8

SYN-

R-8x

UOP-

1

UOP-

2

UOP-

3

UOP-

4

UOP-

HRJ-5

FT-SPK or Bio-SPK Jet Fuel

Mas

s %

(iso+n) Paraffincyclo-Paraffiniso-Paraffinn-Paraffin

FT-SPK

* identifies data from CRC project #AV-2-04a. GCxGC data for the UOP-1 to UOP-4

Figure 2-1. Carbon Chemistry of Neat FT and Bio-SPKs. The carbon chemistry of several neat FT-SPKs and Bio-SPKs is shown in Figure 2-1 whereas Table 2-8 shows the ratio of branched paraffins (i) over normal paraffins (n) in the SPK samples.

SAS SHE SYN UOP Sample

GTL-1* GTL-2* IPK* GTL* S-8* 1 2 3 4

i/n 0.4 2.8 72.9 1.3 4.8 8.0 8.4 8.7 7.2

* identifies data from CRC project #AV-2-04a FT-SPK

Table 2-8. Analysis of Neat SPK Samples. The Bio-SPKs are very consistent and are mainly composed of iso-paraffins. This is further illustrated in Figure 2-2. The paraffins chain length of the neat UOP-1 to UOP-4 Bio-SPKs varies from C9 to C15 with a majority of iso-paraffins.


0

5

10

15

20

25

n-7iso

-8 n-8iso

-9 n-9

iso -1

0n-1

0

iso -1

1n-1

1

iso -1

2n-1

2

iso -1

3n-1

3

iso -1

4n-1

4

iso -1

5n-1

5

iso -1

6n-1

6

iso -1

7n-1

7iso

-18

Carbon distribution

Wt.

%

UOP-1UOP-2UOP-3UOP-4

Figure 2-2. Carbon Chain Distribution of Neat Bio-SPK Samples

CHN analysis per ASTM D529118 was performed on the neat SPK samples. Table 2-9 shows the CHN elemental analysis results. The Bio-SPK samples are pure hydrocarbons with a high level of saturation. Hydrogen content can also be determined by low resolution NMR following the ASTM D370119 test method.

SAS SHE SYN UOP GTL-1 GTL-2 IPK SPK R-8 R-8x S-8 1 2 3 4 HRJ-5

% C 84.7 84.5 84.3 85.0 86.3 84.9 84.0 85.4 85.0 85.4 85.7 84.5 % H 15.5 15.4 15.4 15.7 14.1 15.3 15.6 15.1 15.0 15.5 15.1 15.5 % H* 15.2 15.5 15.6 15.5 N/A N/A 15.2 N/A 15.2 15.3 15.4 N/A % N - - - - - - -


Description Method Unit UOP-2B50 UOP-3B50 UOP-4B50 UOP-HRJ-5B50M Paraffins 58.1 63.5 64.50 62.70 Monocycloparaffins 16.5 24.6 24.90 23.50 Dicycloparaffins 11.2 0.0 0.00 0.00 Tricycloparaffins 2.9 0.0 0.00 0.00 TOTAL SATURATES 88.7 88.1 89.40 86.20 Alkylbenzenes 5.3 7.3 6.40 8.10 Indanes/Tetralins 3.0 3.5 3.40 3.90 Indenes 0.6 0.0 0.00 0.20 Naphthalene 0.4 0.4 0.30 0.40 Naphthalene, Alkyl 1.6 0.6 0.30 1.00 Acenaphthenes 0.2 0.0 0.10 0.10 Acenaphthylenes 0.2 0.1 0.10 0.20 Tricyclic Aromatics 0.0 0.0 0.00 0.00 TOTAL AROMATICS

D2425 mass%

11.3 11.9 10.60 13.90 Table 2-11. Hydrocarbon Types by ASTM D2425

ASTM D2425 is a complicated method that was not originally developed for synthetic fuels. Some discrepancies were observed in the D2425 and GCxGC results. D2425 results are higher (in red in the previous table) than the real values for cycloparaffins. It is now believed that in D2425 test method, the isoparaffins content contributes to the cycloparaffins value due to a specific ion overlap (see 2.2.1.1 for more information). Results obtained by GCxGC are shown in Table 2-6 and Table 2-32.

When blended up to 50% (v) with petroleum-based jet fuels, the Bio-SPK blends have essentially the same physical properties and the same carbon distribution as typical jet fuels.

2.2.1.2 Trace Materials The amount of oxygen containing species is very low in the Bio-SPKs. It was quantified by UOP-730 method20. Otherwise, organic carbonyls can be determined photometrically per ASTM E 411 test method21. For alcohols determination, UOP 656 or EPA 8015B test methods were used. For phenols, EPA 8270C test method and for esters EPA 8260B test methods were used. For inorganics characterization, ASTM D462922 test method allows determination of the trace total nitrogen naturally found in liquid hydrocarbons by thermal oxidation. For Trace Elements analysis (Cu, Zn, Fe, Va, Ca, Li, Pb, P, Na, Mn, Mg, K, Ni, Si), the Bio-SPK samples were analyzed by ICP-AES (inductively coupled plasma-atomic emission spectroscopy) following the ASTM D711123 or UOP-389 test method. The inductively coupled plasma is used to vaporize the sample and produce ions and excited atoms that emit radiations that are characteristic of each element. The intensity of the emission will be proportional to the concentration of the particular element. For copper content determination, it is also possible to use atomic absorption spectrometry per the ASTM D673224 test method.

SYN UOP Method Description Unit R-8 R-8x HRJ-5 HRJ-5B50M EPA 8015B Alcohols ppm


2.2.1.2.1 Neat SPKs

From Table A1.2 of ASTM D7566 HSPK EER SAS SHE SYN UOP Method Description Unit Limits 1 GTL-1 GTL-2 IPK SPK R-8 R-8x S-8 1 2 3 4 HRJ-5 Hydrocarbon Composition D2425 Cycloparaffins mass % 15 (max) 18.4 N/A N/A N/A N/A 8.90 11.2


EER ENE SAS SHE SYN UOP Metals (ppm) 1 1 GTL-1 GTL-2 IPK SPK R-8* R-8x* S-8 1 2 3 4 HRJ-5 Aluminum


2.2.1.2.2 50% (v) SPK Blends

SHE SYN UOP Method Description Unit SPKB50M R-8B50M S-8B50M 2B50 3B50 4B50 HRJ-5B50M D3242 Acidity mg KOH/g 0.003# 0.003 0.005# 0.002 0.002 0.001 0.009 D3227 Sulfur, Mercaptan mass %


Metals Jet A (ppb) JP-5* (ppb) JP-8 (ppb) Aluminum ND 2144 9360 Barium 3 9 38 Calcium 555 5256 31120 Chromium 26 9 18 Copper 5 82 6 Iron 210 210 1144 Lead 11 5 10 Magnesium ND 1056 5840 Manganese 6 10 25 Nickel ND 6 6 Niobium ND ND 2 Potassium ND 118 207 Scandium 11 12 11 Selenium ND ND 21 Strontium 12 70 351 Sulfur 1220 450 1690 Tin 10 48 102 Titanium 100 35 1056 Vanadium ND 3 18 Zirconium 16 14 39

* JP-5 values shown are the higher of two JP-5 sample values. ND = Not Detected

Table 2-18. Principal Elements Detected in Jet Fuels from US Navy Technical Report No. 184525

2.2.2 Bulk Physical and Performance Properties

2.2.2.1 Boiling Point Distribution The boiling point distribution by distillation per ASTM D8626 was performed on all the samples and a comparison was made to data published in the CRC World Survey for minimum and maximum values. For the simulated distillation data, GC (Gas Chromatography) data were collected according to ASTM D288727.

2.2.2.1.1 Neat SPKs SPK Fuel T50 T10 (oC) T90 T10 (oC)

EER-1 31 66 SAS-IPK* 7 29 SAS-GTL-1* 17 40 SAS-GTL-2* 30 60 SHE-GTL* 7 22 SYN-R-8 48 85 SYN-R-8x 37 84 SYN-S-8* 39 89 UOP-1 24 64 UOP-2 19 62 UOP-3 20 59 UOP-4 23 69 UOP-6 39 89 UOP-7 20 51 UOP-8 39 57 UOP-9 38 79 UOP-11 25 59 UOP-12 23 54 UOP-HRJ-5 18 40 UOP-SOL-1 37 95 CRC World Fuel Survey* 14 to 42 55 to 85

*Data from CRC project # AV-2-04a FT-SPK

Table 2-19. Slope of the Boiling Point Curves for Neat SPKs


The boiling point distribution of the neat SPK fuels in Figure 2-3 shows that there is a continuous distribution of hydrocarbons in these samples.

120

140

160

180

200

220

240

260

280

0 10 20 30 40 50 60 70 80 90 100Mass %

T (o

C)

UOP-1UOP-3UOP-4

Figure 2-3. BP Distribution of SPK Fuels by D2887

Table 2-20 contains D2887 values converted to D86 values as required in the ASTM D7566 specification for aviation fuel containing synthesized hydrocarbons. Table 2-21 contains the actual D86 values. The values deviate the most at the ends of the BP distributions.

UOP-1 UOP-2 UOP-3 UOP-4 Mass % (C) IBP 162.6 162.8 164.5 164.1 5 162.2 162.5 167.9 163.1 10 162.3 163.1 167.9 164.4 20 167.2 167.8 171.8 168.7 30 171.7 172.6 175.7 173.3 50 186.4 187.1 188.3 186.6 70 200.6 201.3 200.6 203.2 80 211.5 211.9 210.8 216.7 90 226.0 226.2 226.6 233.2 95 238.4 238.6 241.6 245.2 FBP 251.2 251.6 254.9 256.1

Table 2-20. Calculated D86 Values from D2887 Data for Neat Bio-SPKs

EER-1 SYN-R8 SYN-R8x UOP-1 UOP-2 UOP-3 UOP-4 UOP-HRJ-5 UOP-SOL-1 Mass % (C)

IBP N/A 156.4 153.6 N/A N/A N/A N/A 192.0 130.9 5 N/A 171.7 167.2 N/A N/A N/A N/A 198.5 N/A

10 173 177.7 171.5 163 165 168.5 165 200.5 164.9 15 N/A 181.8 175.9 N/A N/A N/A N/A 203.0 N/A 20 N/A 188.3 180.5 167 169 171.5 168 205.0 172.8 30 N/A 196.8 189.0 N/A N/A N/A N/A 208.5 N/A 40 N/A 207.1 199.3 N/A N/A N/A N/A 212.5 N/A 50 204 217.5 208.8 183 184 186 184 218.0 201.8 60 N/A 227.7 219.0 N/A N/A N/A N/A 222.0 N/A 70 N/A 238.7 229.5 N/A N/A N/A N/A 227.0 N/A 80 N/A 250.5 241.1 N/A N/A N/A N/A 233.0 N/A 90 239 263.0 255.6 224.5 226 225 232 240.0 259.6 95 N/A 270.9 266.0 N/A N/A N/A N/A 245.5 N/A

FBP 254 273.9 267.9 242 248 248 248 255.5 296.7 Table 2-21. Actual D86 Results for 100% SPK Fuels


0

50

100

150

200

250

300

350

0 10 20 30 40 50 60 70 80 90 100

Percentage Recovered

Tem

pera

ture

(oC

)

Specification LIMITSAS-IPKSAS-GTL-1SAS-GTL-2SHE-GTLSYN-S-8EER-1SOL-1SYN-R8SYN-R8xUOP-1UOP-2UOP-3UOP-4UOP-HRJ-5

Spec Limit:max 205oC at 10% recovery


CRC Project # AV-2-04a

Figure 2-4. BP Distribution of Neat SPKs

2.2.2.1.2 50% (v) SPK Blends

0

50

100

150

200

250

300

350

0 10 20 30 40 50 60 70 80 90 100Percentage Recovered

Tem

pera

ture

(oC

)

Specification LIMITSasol IPK Jet A-1Sasol GTL-1 Jet ASasol GTL-2 Jet AShell GTL JP-8Syntroleum S-8 JP-8UOP-2B50UOP-3B50UOP-4B50UOP-HRJ-5B50M



CRC Project # AV-2-04a

Figure 2-5. BP Distribution of SPK Blends


SPK Fuel T50 T10 (oC) T90 T10 (oC) SAS-GTL-1 / Jet A* 22 68 SAS-GTL-2 / Jet A* 32 70 SAS-IPK / Jet A-1* 14 49 SHE-GTL / JP-8* 17 45 SYN-S-8 / JP-8* 36 83 SYN-R-8B50M 33 77 UOP-2B50 29.5 69 UOP-3B50 19.9 56.5 UOP-4B50 23.5 57.5 UOP-HRJ-5B50M 17.2 43.8 CRC World Fuel Survey* 14 to 42 55 to 85

*Data from CRC project # AV-2-04a FT-SPK 50% (v) blends approved

Table 2-22. Slope of the Boiling Point Curves for 50% (v) SPK Blends

SAS SHE SYN UOP GTL-1B50* GTL-2B50* IPK-B50* SPK-B50M* R-8B50M S-8B50M* 2B50 3B50 4B50 HRJ-5B50M Description

oC oC oC oC oC oC oC oC oC oC 10% recovered 160 183 183 171 179 170 171.0 170.4 170.5 195.5 50% recovered 182 215 197 188 212 206 200.5 190.3 194.0 212.7 90% recovered 228 253 232 216 256 253 240.0 226.9 228.0 239.3 Final boiling point 257 265 257 236 270 275 258.0 246.8 248.5 253.7 Distillation residue, % 1.2 1.0 1.0 1.0 1.4 1.3 1.2 1.2 1.2 1.4 Distillation loss, % 0.2 0.2 0.5 0.3 1.4 1.1 0.2 0.4 0.2 1.0

*Data from CRC project # AV-2-04a FT-SPK 50% (v) blends approved

Table 2-23. BP Distribution of B50 SPK Blend Samples per ASTM D86

Temperature in oC UOP-3 Jet A-1 UOP-3B50 Initial Boiling Point 157.6 153.1 155.7 10 % Recover 168.2 169.6 168.3 20 % Recover 171.6 176.1 173.3 50 % Recover 184.3 193.4 189.1 90 % Recover 228.4 228.7 228.2 Final Boiling Point 239.1 240.6 240.3

Table 2-24. BP Distribution of B100 and B50 Bio-SPK and Jet A-1 per ASTM D86


2.2.2.2 Vapor/Liquid Ratio The temperature dependence of the true vapor pressure of several samples was measured using ASTM D637828 test method.

2.2.2.2.1 Neat SPKs

0

1

2

3

4

5

6

0 20 40 60 80 100 120 140 160

Temperature (oC)

Vapo

r Pre

ssur

e (p

sia)

UOP-4

UOP-HRJ-5

SAS-IPK

SYN-R-8

SYN-R8x

T-1, TS-1, Russian

CRC Handbook of Aviation FuelProperties - Jet A, Jet A-1, JP-8

Jet A, Jet A-1, JP-8

Figure 2-6. Vapor Pressure vs. Temperature of Neat SPKs

UOP-HRJ-5 has a lower vapor pressure than typical Jet A; it was produced to meet the JP-5 flash point specification.

2.2.2.2.2 50% (v) SPK Blends

0

1

2

3

4

5

0 20 40 60 80 100 120 140 160

Temperature (oC)

Vapo

r Pre

ssur

e (p

sia)

UOP-2B50

UOP-3B50

UOP-4B50

UOP-HRJ-5B50M

SYN-R-8B50

T-1, TS-1, Russian

CRC Handbook of Aviation FuelProperties - Jet A, Jet A-1, JP-8

Jet A, Jet A-1, JP-8

Figure 2-7. Vapor Pressure vs. Temperature of 50% (v) SPK blends


Vapor pressure of both FT-SPK and Bio-SPK jet fuels are very similar. Their values are between the values published in the CRC Handbook of Aviation Fuel Properties for Jet A, Jet A-1 and JP-8 and the value of a TS-1 Russian jet fuel29. The data at low temperatures are being investigated since it seems to deep below TS-1 values. Note that FT-SPK and Bio-SPK jet fuels behave the same way. All samples of SPKs used in this report (FT or Bio) are being retested along Jet A and TS-1 samples. Two independent labs are running the tests of each sample. The results will be amended to this report as soon as available.

2.2.2.3 Thermal Stability The thermal stability of the Bio-SPKs was checked by fuel thermal stability test, formerly known as JFTOT, ASTM D 324130 test method, Appendix X.2. The breakpoint is the highest control temperature at which the fuel meets tube rating and DP specification requirements.

2.2.2.3.1 Neat SPKs

Neat SPK Fuel Temperature, oC Filter dP, mm Hg Tube deposit Pass/Fail LIMIT 325 25 (max)


with the tube deposit rating done at 345oC, which was determined to be the breakpoint of the fuel (see Table 2-25).

2.2.2.3.2 50% (v) SPK Blends

Sample Temperature, oC Filter dP, mm Hg Tube deposit Pass/Fail LIMIT 260 25 (max)

Bio-SPK Research Report 2010 v5

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