Ohio Center for Intelligent Propulsion and Advanced Life Management

1. Alternative Fuels Research: Practical Applications and Foundational Questions • Ohio Center for Intelligent Propulsion and Advanced Life Management • Ohio Third Frontier Program Review Heinz J. Robota, Ph.D. Ohio Research Scholar in Alternative Fuels Group Leader: Alternative Fuels Synthesis University of Dayton Research Institute University of Cincinnati 14 May 2013

2. Overview • Alternative Fuels in Aviation • Fuel types and specifications • Facilities • Practical Scale Preparations • Fischer-Tropsch Synthetic Paraffinic Kerosene • Unique “single carbon number, narrow boiling” fuels • True “drop-in” renewable Jet-A • Foundational Research • Algae oil to jet and diesel • Kinetics of stearic acid deoxygenation • Summary

3. The Origination of the Assured Aerospace Fuels Research Facility Generate practical sample quantities of jet boiling range material for evaluation and demonstration

4. Alternative Fuels Approved by “type” for use in a blend with petroleum fuel • USAF leadership from properties, characteristics, specifications, through flight approval – commercial aviation now implementing slowly • Approved or nearly approved fuels categorized as “Synthetic Paraffinic Kerosene” (SPK) • Aliphatic hydrocarbons – negligible aromatic content • Highly isomerized alkanes – for low temperature properties • Type Specifications accommodate the peculiarities of the fuel chemical constituents • Fischer-Tropsch SPK – First type to be approved • Hydrotreated Renewable Jet (HRJ) or Hydrotreated Esters and Fatty Acids (HEFA) – second to be approved • Spec has added requirements related to: Gum, FAME content • Nearly approved Alcohol-to-Jet (ATJ) – allows higher cycloparaffins • Otherwise, these specs are the SAME

5. Shroyer Park Center Catalyst Preparation and Testing Capabilities 4 Fixed bed reactors with concurrent liquid and gaseous feed 2 Fixed bed FT synthesis reactors and 2 CSTRs available for swap Continuous off-gas monitoring with on-line GC Micromeritics ASAP 2020 textural analysis and chemisorption analysis system being installed Surface Area Pore Volume Pore size distribution Metal Catalyst dispersion Mix-muller for 1-3 kg preparation of extrudable catalyst/binder aggregate 1” laboratory extruder for making shaped catalyst for use in AAFRF or other practical-scale fixed bed reactors reactors High resolution FTIR with heated multi-path gas cell for trace gas contaminant analysis – NH3,HCN, CO, CO2 Usable for condensed phase research as well

6. Facilities: Assured Aerospace Fuels Research Facility - AAFRF • What Is The AAFRF? • SPU, Facility and Team • Skilled and experience team (USAF, UDRI and BMI) • Answer practical questions about fuels from alternative sources • Producing practical quantities of demonstration fuelfor testing and demonstrating synthetic routes • Assess catalyst –related technology through formulation and evaluation. Lab at Shroyer Park Center

7. AAFRF-SPU Designed with FT Upgrading in Mind

8. AAFRF Commissioned making SPK from Genuine F-T Wax AAFRF SPK properties are nearly identical to other non JP-8 jet fuels • Validated design criteria • Validated catalyst function • Required Heat Trace everywhere • Distillation heater required higher • output than original design • Validated automation system • Ready for production research!

9. Preparing a C14 narrow boiling SPK: Maximizing Isomer Yield Synthetic approach demonstrated at SPC Lab scale – in house catalysts scaled to multi kg lots Outstanding performance scalability from lab to AAFRF scale Fed roughly 2200 gal n-C14 - recovered 1700 gal of mixed C14 isomers

10. Preparing a C14 narrow boiling SPK: Final Product by Distillation A consolidated 500 gal batch with freezing point of -41.7 °C – meets Jet-A Specification Isomer distribution is different from a solvent-dewaxed product in a desirable way – multi-branched isomers dominate Distillation Gradient T90-T10 = 17 °C – meets the narrow boiling target From concept discussions to fuel delivery in 18 months A successful campaign and project!

11. Supporting Commercialization: Finishing a Prospective True Renewable “Drop-in” Jet-A 1750 gallons of “CH Crude” delivered for Total Acid Number (TAN) reduction and separation of the Jet-A Specification –compliant fraction Delivered TAN 140 mg/g Required reduction to <0.10 mg/g Distilled fraction to meet Jet-A Specification

12. Supporting Commercialization: Finishing a Prospective True Renewable “Drop-in” Jet-A Delivered 525 gallons of a theoretical 565 max, >90% Cumulative TAN 0.005 mg KOH/g – an effective overall conversion of 99.996% !! First use of a sulfided catalyst in the system Fuel met all applicable JET-A specifications Flash point and Freezing point set the bounds on allowable composition

13. Converting Algal Oil to Fuels: First to n-Alkanes Algae provided by USAF from Phycal production Output of a Third Frontier development program Processed ~ 2.5 L of algal oil Product Alkanes reflect oil composition and a changing catalyst selectivity with time-on-stream

14. Converting Algal Oil to Fuels: n-Alkanes to Fuel All methods and catalysts used are readily scalable n-C17 n-C18 n-C15 n-C16 Deoxygenated alkane mixture hydro-converted to isomers and cracked products with Pt/US-Y A Practical Diesel Fuel Selective removal of n-alkanes improves cold weather flow – Arctic Grade Diesel Fuel

15. Elucidating Reaction Kinetics of a Complex Reaction Network Fitting power law kinetics with the effects of T, concentration of reactants Rigorous control of all reaction variables to produce reproducible reaction rates allowing parameter extraction

16. Summary • Established a laboratory infrastructure to make and investigate fuel-making catalysts and catalyst processes • Brought to operation the AAFRF-SPU within the design envelope by making genuine Fischer-Tropsch SPK • Successfully produced two unique research fuels for composition-property research • Delivered 525 gallons of genuine drop-in renewable Jet-A for an industrial collaborator • Established foundational research related to liquid fuel-making catalytic chemsitries

17. Acknowledgements This research was supported, in part, by the U. S. Air Force Cooperative Grant Numbers F33615-03-2-2347 and FA8650-10-2-2934 with Mr. Robert W. Morris Jr. serving as the Air Force Grant Monitor. The research was also sponsored by the State of Ohio Subrecipient Award No. COEUS # 005909 to the University of Dayton (Dr. Dilip Ballal as the Grant Monitor) under the “Center for Intelligent Propulsion and Advanced Life Management,” program with the University of Cincinnati (Prime Award NO. TECH 09-022). We gratefully acknowledge this support. Thank you to UDRI personnel: Steve Zabarnick, Matthew de Witt, Rich Striebich, Linda Shafer, Ryan Adams, Zachary West, Dave Thomas, Gordon Dieterle, James Shardo, Jerry Grieselhuber, Jeff Coleman, Jeff Unroe, Alan Wendel, Dennis Davis, Ted Williams, David Gasper, Scott Breitfield, Rhonda Cook, Zachary Sander, Jhoanna Alger, Andrew Palermo, Albert Vam, Roger Carr, Becki Glagola, Sam Tanner, Drew Allen Thank you to Battelle personnel: Satya Chauhan, Eric Griesenbrock, Nick Conkle, Grady Marcum, Bill Jones, George Wrenn, Sarah Nejfelt, Cory Kuhnell, Stephen M. Howe, Erik Edwards, J. Boyce, C. Lukuch Thank you to Air Force Personnel: Robert W. Morris, Jr., Lt. Mark Roosz, Lt. Adam Parks, Milissa Flake Thank you to UTC Personnel: Jennifer Kelley, Steve Procuniar